JP2002123038A - Electrophotographic toner and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a toner less in its odor and odor produced at the fixing time and excellent in storage stability, fixability and electrostatic chargeability by effectively deodorizing/removing trace odorous substances produces by the decomposition of a part of the toner due to the slightly remaining odorous substances and the storage environment at the manufacturing time in the ordinary method for manufacturing the toner. SOLUTION: In the method for manufacturing the toner, the toner particles containing at least a resin prepared by polymerizing polymerizable monomers in a water-based medium and coloring agent are treated with a deodorant containing a component extracted from plant before the toner particles are separated from the water-based medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner used in a copying machine, a printer, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Impurities contained in a toner for developing electrostatic images (hereinafter simply referred to as toner) used in electrophotography and the like, particularly components having a low-molecular-weight fragrance, are used in a toner container when the toner is used. It causes inconvenience such as giving an unpleasant odor when opened. Further, as a method of fixing the toner on the copy paper surface in the fixing step, a pressure fixing method, a heat fixing method, or the like is used. Further, as the heat fixing method, for example, there are an oven fixing method, a flash fixing method, a pressure fixing method, a heating roller fixing method, and the like. In an electrophotographic copying machine, the heating roller fixing method is widely used. Have been. This method has extremely good thermal efficiency when the surface of the heating roller and the image of the sheet to be fixed are fused onto the sheet to be fixed, and can quickly fix the image. Particularly, this method is extremely useful as a fixing method during high-speed copying. It is valid.

[0003] However, in this method, since a toner image is heated, a trace component contained in the toner is released into the atmosphere, which may cause an unpleasant odor to the user.
Further, in recent years, with the miniaturization of copiers and printers, offices and the like have more and more opportunities to use them close to each other. In addition, the chances of use in ordinary households are increasing, and as a result, the odor emitted from the toner is more likely to cause discomfort to the user than ever before.

As one of the causes of the bad smell generated from the electrophotographic apparatus, ozone was generated by corona discharge. However, a contact charging method such as roller charging or brush charging, or a corona discharger which minimized ozone generation was used. Ozone odor has been drastically reduced by the technical innovation of the related art, and the toner odor relatively caused by the toner often gives discomfort. In addition, in order to adsorb ozone, odor, etc., the main unit may be provided with a filter, etc., but these are disadvantageous in terms of production cost, and in order to maintain the deodorizing function,
There is also trouble such as periodic replacement.

As another method of reducing the odor derived from these toners, there is a method of reducing impurities in a binder resin. For example, JP-A-64-707
No. 65, No. 64-88556, JP-A-8-3
No. 28311 proposes a reduction in odor by reducing residual monomers in a binder resin.
JP-A-7-104515, JP-A-7-104514, and the like disclose that reducing the volatile components contained in the resin is not sufficient, and that during the toner manufacturing process, a small amount of chemically contained raw materials is not included. Since volatile matter generated by the decomposition of a stable substance causes odor, a technique for removing the odor of the raw material is disclosed as a countermeasure against the odor of the final toner product as a whole.

In Japanese Patent Application Laid-Open No. 8-171234, an attempt has been made to reduce the content of benzaldehyde by assuming that the odor-causing substance is an oxidation product of benzaldehyde contained in the toner. On the other hand, in Japanese Patent Application Laid-Open No. 9-230628, while reducing the amount of alkyl mercaptan (one of the substances causing odor), which is a molecular weight controlling agent for resin and indispensable for the basic performance of toner, By suppressing the amount to the minimum necessary amount, the odor is improved, and at the same time, a device is devised to prevent the adverse effect on the fixability.

Japanese Patent Application Laid-Open No. 3-105350 discloses an attempt to add an alkylbetaine compound to a toner as a substance that reacts and adsorbs odorous substances. However, due to the structure of the compound, other effective toner components are used. Is inevitable, which results in, for example, impairing the basic quality such as chargeability of the toner. Furthermore, Japanese Patent Application Laid-Open No. H2-240663 describes a method in which a deodorant and a toner are brought into contact with each other for 5 hours or more in a pulverizing and classifying step to deodorize. The odor generated after the end of the production is not reduced.

Further, in any of the above methods, since the required amount of odorous substances that can be perceived by humans is extremely small, no matter how the causative substances are removed, from the end of production to opening and use by the user. In the meantime, there are odor substances that are very slightly volatilized and trace amounts of odor substances generated by the decomposition of a part of the toner components depending on the storage environment after the production, and these can be easily perceived.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem that in a normal toner production method, a very small amount of odorous substances that remain due to a very small amount of odorous substances and a trace amount of toner components that are partially decomposed due to the storage environment during production. Effectively removes odorous substances
An object of the present invention is to provide a toner and a method for producing a toner, which have reduced odor of the toner itself and odor at the time of fixing, and have excellent storage stability, fixing property and chargeability of the toner.

[0010]

The above object of the present invention has been attained by the following constitutions.

1. Before separating the toner particles containing the resin and the colorant formed by polymerizing at least the polymerizable monomer in the aqueous medium from the aqueous medium, it is treated with a deodorant containing a plant extract component. Toner production method.

2. 2. The method according to claim 1, wherein at least one of the plant extractables is a phytontide.

3. 2. The method according to claim 1, wherein at least one of the plant extraction components is a catechin.

4. A toner characterized in that it is treated with an enzyme-containing deodorant before the toner particles containing a resin and a colorant formed by polymerizing at least a polymerizable monomer in an aqueous medium are separated from the aqueous medium. Production method.

[0015] 5. A method for producing a toner, comprising: treating a resin formed by polymerizing at least a polymerizable monomer in an aqueous medium and a toner particle containing a colorant with a metal phthalocyanine-based deodorant before separating the toner particles from the aqueous medium. Method.

6. Before separating the resin particles formed by polymerizing at least the polymerizable monomer in the aqueous medium and the toner particles containing the colorant from the aqueous medium, treating with an artificial enzyme deodorant containing metal phthalocyanines. A method for producing a toner.

[7] A method for producing a toner, comprising: treating a resin formed by polymerizing at least a polymerizable monomer in an aqueous medium and toner particles containing a colorant with a microbial deodorant before separating the toner particles from the aqueous medium. .

[8] Before separating the resin particles formed by polymerizing at least the polymerizable monomer in the aqueous medium and the toner particles containing the colorant from the aqueous medium, treatment with a deodorant liquid dissolved or dispersed in water is required. A method for producing a toner.

9. Before separating the toner particles containing the resin and the colorant formed by polymerizing at least the polymerizable monomer in the aqueous medium and separating the toner particles from the aqueous medium, treatment with a porous powder or a nonwoven fabric to which a deodorant is fixed is required. A method for producing a toner.

[10] At least a polymerizable monomer is polymerized in the presence of a compound having a mercapto group in an aqueous medium.On the surface of the toner particles containing the resin and the colorant formed through the step of deodorizing the plant deodorant-containing component, A toner characterized by being adsorbed.

11. At least the enzyme-containing deodorant is adsorbed on the toner particles containing the resin and the colorant formed through the step of polymerizing at least the polymerizable monomer in the aqueous medium in the presence of the compound having a mercapto group. A toner characterized in that:

12. At least a metal phthalocyanine-based deodorant was adsorbed on the surface of toner particles containing a resin and a colorant formed through a step of polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group. A toner characterized in that:

13. At least a polymerizable monomer is polymerized in an aqueous medium in the presence of a compound having a mercapto group, and on the surface of a toner particle containing a resin and a colorant, an artificial enzyme containing metal phthalocyanines is deodorized. A toner characterized by adsorbing an agent.

14. At least a microbial deodorant is adsorbed on the surface of toner particles containing a resin and a colorant formed through a process of polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group. A toner characterized by the following.

Hereinafter, the present invention will be described in detail. (Plant Extraction Component) In the invention according to claim 1, the polymerizable monomer is polymerized in an aqueous medium, and before the toner particles containing at least the resin and the colorant are separated from the aqueous medium,
It is characterized by being treated with a deodorant containing a plant extract component.

In the present invention, the plant extract refers to an extract derived from a plant, an extract, or a compound having a structure equivalent to that of a plant extract dispersed in water or the like.
In the present invention, as the deodorant substance related to the plant extract component, those that deodorize sulfur-based malodorous components are preferable, and for example, plant extracts such as green tea extract, persimmon condensed tannin and bamboo extract are preferable. It has the effect of chemically decomposing hydrogen sulfide, methyl mercaptan, and the like to convert it to odorless molecules, or to wrap (enclose) these odorous molecules to make it odorless.

When the deodorant containing the plant extract of the present invention is produced from green tea, the ground leaf of tea leaves is soaked in ethanol, and then the catechins, vitamins, sugars and enzymes obtained therefrom are obtained. By filtering and concentrating the ethanol extraction solution containing, the deodorant containing the plant extract component according to the present invention can be obtained. More specifically, the fresh leaves of the tea leaves are ethanol of 80 ° C. or less, for example, 50 to 70 ° C.
This solution contains ethanol-soluble components and water-soluble components contained in fresh tea leaves. In the extraction of fresh leaves of tea leaves with ethanol, the ethanol extract contains (-)-
Epicatechin (EC), (-)-epigallocatechin (E
gC), flavanols such as (-)-epicatechin gallate (ECg) and (-)-epigallocatechin gallate (EGCg), enzymes such as oxidoreductase, transferase, hydrolase and isomerase, flavonols Kind, for example,
Flavones, isoflavones, flavonols, flavanones,
Flavor reels, Auron, Anto anidine, Chalcone,
The extract contains substantially the same components as green tea extract containing dihydrochalcone and the like and glycosides of flavonols, caffeine, amino acids, flavandiols, polysaccharides, proteins, vitamins, and the like. The fresh leaf component of tea leaves varies depending on the weather, temperature, harvest time and harvest location, so it provides a uniform and stable deodorant duration as a deodorant, and also enhances the deodorant effect and deodorizing power of the deodorant. Therefore, it is preferable to add the synthesized and purified vitamin C and vitamin B1 to the ethanol extract at 1 to 2% by mass of the solid content.

The deodorant according to the present invention is an alcohol solution such as ethanol containing catechins, vitamins, saccharides and enzymes, and can further contain an extraction residue of alcohol from fresh leaves of tea leaves. Therefore, the deodorant according to the present invention can be produced by immersing a crushed material of fresh tea leaves in alcohol and extracting components of the tea leaf contained in the fresh leaves.

Other specific examples of deodorants containing plant extract components include trees such as cypress, Aomori hiba, beech, cedar, camphor, eucalyptus, etc., herbs, mustard, wasabi, lemon, karin, peppermint, clove, Ceylon Nikkei,
Bamboo, Iriomote thistle rhizome, or Yaeyama palm root and the like, and an extract or an extract component can be obtained by treating these plants by crushing, squeezing, boiling, or steam distillation. Specific examples of plant-derived extract components or synthetic compounds having a structure equivalent to the plant extract component include tropolones such as hinokitiol, α
-Pinene, β-pinene, camphor, menthol, limonene, borneol, α-terpinene, γ-terpinene,
Monoterpenes such as α-terpineol, terpinen-4-ol and cineol; sesquiterpenes such as α-casinole and t-murol; polyphenols such as catechin and tannin; naphthalene derivatives such as 2,3,5-trimethylnaphthalene , Citronellol and other long-chain aliphatic alcohols, cinnamaldehyde, citral,
Aldehydes such as perilaldehyde, allyl compounds such as allyl isothiocyanate and the like can be mentioned. Wood vinegar obtained by steaming trees can also be used in the present invention. When a plant-derived extract component or a compound having a structure equivalent to that of the plant extract component is insoluble in water, the extract component can be used by dispersing in water using a dispersant such as a surfactant.

As commercially available plant deodorant deodorants, for example, F118 (manufactured by Fine2 Co., Ltd.) and Delsen (manufactured by Aizen Chemical Industry Co., Ltd.) are preferably used.

The invention according to claim 2 is characterized in that at least one of the plant extractables is a phytontide.

The phytoncide-based deodorant is mainly composed of a plant extract containing phytoncide, and has a molecular weight of 15,000 to 2,300,000 extracted from conifers.
0 natural polymer substances, anionic activators, glycols,
Manufactured by adding a special activator, a host compound, and the like, the effect is to completely decompose odor components chemically by the neutralization inclusion method and convert it to another substance. As a commercial product, Bio Dash D-200 (manufactured by Daiso) is preferably used.

(Enzymatic deodorant) In the invention according to claim 4, the polymerizable monomer is polymerized in an aqueous medium, and before the toner particles containing at least the resin and the colorant are separated from the aqueous medium, It is characterized in that it is treated with a deodorant containing an enzyme.

Many biological oxidases, particularly certain metal-containing enzymes, have a function of oxidatively decomposing ammonia, amines, hydrogen sulfide, mercaptans, indole, carbonyl compounds and the like. That is, since many odor molecules have mobile hydrogen, they are dehydrogenated and oxidized,
Deodorization becomes possible by dimerization, water solubility and non-volatility.

Specific examples of enzymes having a deodorizing effect include:
Examples thereof include enzymes such as tacarase, amylase, protease, lipase, papain, chymopapain, and pepsin. The tacarase enzyme contains hematoporphyrin, binds to an apoprotein, iron is in a trivalent spin electronic state, and histidine imidazole nitrogen of the protein is coordinated to the fifth coordination site. In addition, as a commercially available enzyme-based deodorant,
Bio C (manufactured by Consol Corporation) and Bio Dash P-500 (manufactured by Daiso) are preferably used.

(Metal Phthalocyanine and Artificial Enzyme Deodorant Using It) In the invention according to claim 5, a metal phthalocyanine deodorant is used. In the invention according to claim 6, the metal phthalocyanine is It is characterized in that a toner is manufactured using the artificial enzyme-based deodorant contained therein.

A metal phthalocyanine derivative, preferably a carboxyphthalocyanine iron complex, and particularly preferably an octacarboxyphthalocyanine iron iron complex having a catalytic activity similar to that of the natural enzyme tacarase, has an effect of decomposing odor molecules by a reaction mechanism similar to that of tacarase. Having. The molecular structure of the octacarboxyphthalocyanine iron complex is shown below.

[0038]

Embedded image

For example, taking the example of the oxidation mechanism of mercaptan, the following chemical reaction is shown. ^{2R-SH + 2OH - → 2R} -S - + 2H 2 O (1) 2R-S - + 2H 2 O + O 2 → R-S-S-R + H 2 O 2 + 2OH - (2) ( provided that, R: CH ₃ or C ₂ H ₅ ) The thiolate anion generated by the reaction of the above formula (1) coordinates with oxygen to the metal phthalocyanine to become an active species which is a ternary complex, and then coordinates with this active species as shown in the above formula (2). The thiolate aonine is deodorized by dimerization to disulfide. As described above, when metal phthalocyanine is used as a deodorant, 1: the reaction rate is high and the decomposition efficiency is good 2: the reaction proceeds at room temperature 3: there is no concern about environmental pollution due to the water-based reaction 4: cycle Since it is a reaction, it has conditions that are advantageous in decomposing malodor such as long catalyst life.

In the present invention, an artificial enzyme in which a metal phthalocyanine derivative and a polymer compound are ion-bonded is used as a deodorant. As a specific example of the polymer compound, cyclodextrin is preferably used.

(Microbial deodorant) In the invention according to claim 7, the polymerizable monomer is polymerized in an aqueous medium, and the microorganisms are separated from the aqueous medium before the toner particles containing at least the resin and the colorant are separated from the aqueous medium. It is characterized in that it is treated with a system deodorant.

As the microbial deodorant according to the present invention, a deodorant using a microorganism culture solution is used. Examples of the microorganism include at least one microorganism selected from the genus Bacillus, the genus Enterobacter, the genus Streptococcus, the genus Rhizopus, and the genus Aspergillus. Further, microorganisms of the genera Nitrosomonas, Nitrobacter and Pseudomonas are preferably used. The microorganism deodorant is used in an amount of 5 to 10 sugars per 10 parts by mass of these microorganisms.
0 parts by mass, 0.1 to 50 parts by mass of a water-soluble nitrogen compound and 1,000 to 50,000 parts by mass of water at a temperature of 2
After culturing for 15 to 40 hours under the conditions of 0 to 40 ° C. and an oxygen supply amount of 0.02 to 2.0 liter / min, the supernatant or culture solution obtained by centrifugation is dried. If necessary, 20 to 300 parts by mass of a porous powder such as sawdust may be added to the culture solution to support microorganisms. In addition, a liquid aldehyde, specifically, glutaraldehyde may be used together with these microbial deodorants. Mixing with a liquid aldehyde is preferable because the deodorizing effect is further enhanced.

Specific examples of the microorganisms preferably used in the present invention include microorganisms belonging to the genus Bacillus, particularly Bacillus subtilis (B. subti).
lis) [IAM (Institute of App)
lied Microbiology; an abbreviation for a useful strain preservation facility of the Institute of Applied Microbiology of the University of Tokyo; hereinafter similarly abbreviated as 1168], Bacillus natto (B.
tto) [IFO (Institute for Fe
mentation Osaka: Fermentation Research Institute, Japan; abbreviation: hereinafter also abbreviated to this abbreviation) 3009] is suitable, but in addition, Baltis coagulans (B. coagulans) [IAM 1115] and Bacillus macerans (B) .Macerans) [IA
M 1243] can also be used.

Enterobacter (Enterobacter)
er) microorganisms such as E. sakazaki (IAM 12660),
E. agglon
eras) [IAM 12659] and the like.

[0045] Streptococcus
ccus) as the microorganisms of the genus Streptococcus.
S. faecalis [IAM 111
9], Streptococcus cremoris (S. crem)
oris) [IAM 1150] and Streptococcus lactis [IFO 1254].
6] can be used.

Examples of microorganisms (fungi) belonging to the genus Rhizopus include Rhizopus homosaensis [IAM 625].
0], R. oryzae [I
AM6006] can be used.

Aspergillus (Aspergillus)
Examples of the microorganisms belonging to the genus s) include Aspergillus oryzae (IFO 4176) and Aspergillus niger [IFO 406].
6] can be used.

Nitrosomonas
As the microorganism belonging to the genus s), Nitrosomonas europaea (IFO 14298) and the like can be used.

[0049] Nitrobacte
As the microorganism of the genus r), Nitrobacter agilis (N. agilis) [IFO 14297] or the like can be used.

Pseudomonas (Pseudomona)
s) As a genus, Pseudomonas caliophilii [IFO 1295
0], Pseudomonas staccelli (P. statz
eri) [IFO 3773] or the like can be used.

The microbial deodorant according to the present invention contains a dormant microorganism, an organic acid effective for deodorizing, and an enzyme for decomposing organic substances. That is, microorganisms convert sugars and alcohols into organic acids such as lactic acid, citric acid, malic acid, and produce enzymes (amylase, protease, lipase, etc.) to decompose malodor sources (organic substances).

(Deodorant dissolved or dispersed in water) In the invention according to claim 8, the polymerizable monomer is polymerized in an aqueous medium, and toner particles containing at least a resin and a colorant are converted from the aqueous medium. Before separation, treatment is performed with a deodorant solution dissolved or dispersed in water. The deodorant solution according to the present invention contains 50% by mass or more of water, and may further contain an alcohol, a surfactant, an organic acid, and the like.

(Adsorption of Deodorant on the Surface of Toner Particles) The invention according to claims 10 to 14 is characterized in that each deodorant according to the present invention is adsorbed on the surface of toner particles to form a toner.

In the present invention, the deodorant is in a state of being adsorbed on the surface from the viewpoint of maintaining the deodorizing action even when the toner odor component oozes out of the toner during drying or after the sealed packaging. The method of adsorption is not particularly limited, but it is preferable to dissolve or disperse the deodorant in an aqueous medium for polymerizing and salting out and aggregating the toner. In the toner filtration and washing step described below, a surfactant or a salting-out agent is used. After removing the deposits, it is particularly preferable to treat with a high-concentration deodorant liquid. The deodorant concentration to be adsorbed is
It is preferably 0.01 to 10 ppm. 0.01
If it is less than ppm, the persistence of the deodorizing action is low, and if it is more than 10 ppm, the charging characteristics are not stable.

Next, the method for producing an electrophotographic toner according to the present invention will be described. (Toner Production Method) In the method for producing a toner according to the present invention, the polymerization of a polymerizable monomer in an aqueous medium is preferably performed.
There are two features. That is, when forming resin particles (core particles) or a coating layer (intermediate layer) containing a release agent, the release agent is dissolved in a monomer, and the resulting monomer solution is oiled in an aqueous medium. In this method, latex particles are obtained by dispersing droplets, adding a polymerization initiator to the system, and performing a polymerization treatment.

The aqueous medium referred to in the present invention is water 50 to 10
A medium comprising 0% by mass and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include, for example, methanol, ethanol, isopropanol, butanol,
Acetone, methyl ethyl ketone, tetrahydrofuran and the like can be exemplified, and an alcohol-based organic solvent which does not dissolve the obtained resin is preferable.

An example of the method for producing a toner according to the present invention will be described below. The toner manufacturing process mainly includes the following processes.

1: Multi-stage polymerization step (I) for obtaining composite resin particles containing a release agent and / or crystalline polyester in a region other than the outermost layer (center or intermediate layer) 2: Composite resin particles / Fusing step of salting out / fusing the toner particles with the colorant particles to obtain toner particles (II) 3: Filtering the toner particles from the toner particle dispersion system and surfactant from the toner particles And a washing step of removing the washed toner particles, and a step of adding an external additive to the dried toner particles.

Hereinafter, each step will be described in detail. [Multi-stage polymerization step (I)] The multi-stage polymerization step (I) is a step of producing composite resin particles by forming a coating layer made of a monomer polymer on the surface of the resin particles by a multi-stage polymerization method. It is.

In the present invention, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more from the viewpoint of production stability and crushing strength of the obtained toner.

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

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

The method will be described in detail. First, a releasing agent is dissolved in a monomer L to prepare a monomer solution, and the monomer solution is added to an aqueous medium (for example, an aqueous surfactant solution). After oil droplets are dispersed in the system, this system is subjected to polymerization treatment (first stage polymerization).
By doing so, a dispersion of high molecular weight resin particles containing a release agent is prepared.

Next, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the dispersion of the resin particles.
Polymerization treatment of monomer L in the presence of resin particles (second stage polymerization)
Is carried out to form a coating layer made of a low-molecular-weight resin (polymer of monomer L) on the surface of the resin particles.

<Three-stage polymerization method> The three-stage 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 (shell) formed of a low molecular weight resin. This is a method for producing composite resin particles. That is, the composite resin particles obtained by the three-stage polymerization method are composed of a core and two coating layers.

The method will be specifically described. First, a dispersion of resin particles obtained by a polymerization treatment (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). Along with the addition, the monomer solution obtained by dissolving the release agent in the monomer M in the aqueous medium is dispersed in oil droplets, and then the system is subjected to a polymerization treatment (second stage polymerization).
A coating layer (intermediate layer) made of a resin (polymer of monomer M) containing a release agent is formed on the surface of the resin particles (core particles) to form a composite resin particle (high molecular weight resin-intermediate molecular weight resin). )
A dispersion of is prepared.

Next, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the obtained dispersion of the composite resin particles, and the monomer L is subjected to a polymerization treatment in the presence of the composite resin particles. By performing (third stage polymerization), a coating layer made of a low molecular weight resin (polymer of monomer L) is formed on the surfaces of the composite resin particles. In the above method, by incorporating the second-stage polymerization, the release agent can be finely and uniformly dispersed, which is preferable.

As a polymerization method suitable for forming resin particles or a coating layer containing a release agent, an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved is used.
A monomer solution in which the release agent is dissolved in the monomer is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the obtained dispersion, A method in which radical polymerization is carried out in oil droplets (hereinafter, referred to as “mini-emulsion method” in the present invention) can be mentioned, and the effect of the present invention can be further exhibited, which is preferable. In the above method, an oil-soluble polymerization initiator may be used instead of or together with the water-soluble polymerization initiator.

According to the miniemulsion method in which oil droplets are formed mechanically, unlike the usual emulsion polymerization method, the release agent dissolved in the oil phase does not detach, and the resin particles or A sufficient amount of release agent can be introduced into the coating layer.

Here, the disperser for dispersing the oil droplets by mechanical energy is not particularly limited. For example, a stirrer “CLEARMIX” (M) equipped with a high-speed rotating rotor -Technic Co., Ltd.), an ultrasonic disperser, a mechanical homogenizer, a Menton-Gaulin and a pressure homogenizer. Further, the dispersion particle diameter is 1
0 to 1000 nm, preferably 50 to 1000 n
m, more preferably 30 to 300 nm.

As other polymerization methods for forming resin particles or a coating layer containing a release agent, emulsion polymerization methods,
Known methods such as a suspension polymerization method and a seed polymerization method can also be employed. In addition, these polymerization methods are resin particles (core particles) or coating layers constituting the composite resin particles,
It can also be employed to obtain one that does not contain a release agent and crystalline polyester.

The particle diameter of the composite resin particles obtained in the polymerization step (I) was determined by using an electrophoretic light scattering photometer “ELS-80”.
It is preferable that the mass average particle diameter measured using “0” (manufactured by Otsuka Electronics Co., Ltd.) is in the range of 10 to 1000 nm.

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 95-14.
It is preferably in the range of 0 ° C. [Salt-out / fusion step (II)] This salt-out / fusion step (II)
Is an amorphous (non-spherical) by salting out / fusing the composite resin particles and the colorant particles obtained in the multi-stage polymerization step (I) (simultaneous salting out and fusion).
This is the step of obtaining the toner particles.

The term “salting out” as used in the present invention means that the composite resin particles dispersed in an aqueous medium are aggregated by utilizing the action of a salt. In addition, fusion refers to eliminating the interface between resin particles aggregated by salting out. The salting out / fusion in the present invention refers to an action in which two steps of salting out and fusion occur sequentially or are caused to occur sequentially. In order to simultaneously carry out the salting-out and the fusion, the particles (composite resin particles, colorant particles) under a temperature condition not lower than the glass transition temperature (Tg) of the resin constituting the composite resin particles.
Need to be aggregated.

In the salting-out / fusion step (II), internal additive particles (fine particles having a number average primary particle diameter of about 10 to 1000 nm) such as a charge controlling agent are salted out together with the composite resin particles and the colorant particles. / It may be fused. The colorant particles may be surface-modified, and as the surface modifier,
Conventionally known ones can be used.

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

The disperser used for the dispersion treatment of the colorant particles is not particularly limited, but is preferably a stirrer “CLEARMIX (CLEARM) equipped with a high-speed rotating rotor.
MIX) "(manufactured by M Technique Co., Ltd.), an ultrasonic disperser, a mechanical disperser such as a mechanical homogenizer, a Menton-Gaulin, a pressure type homogenizer, and a medium disperser such as a Getzman mill or a diamond fine mill.

For salting out / fusing the composite resin particles and the colorant particles, a salting-out agent (aggregating agent) having a critical coagulation concentration or more is added to the dispersion in which the composite resin particles and the colorant particles are dispersed. ) And heating the dispersion above the glass transition temperature (Tg) of the composite resin particles.

The temperature range suitable for salting out / fusing is (Tg + 10) to (Tg + 50 ° C.), and particularly preferably (Tg + 15) to (Tg + 40 ° C.). Further, in order to effectively perform the fusion, an organic solvent which is infinitely soluble in water may be added.

[Filtration / Washing Step] In this filtration / washing step, a filtration treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above step, Washing treatment for removing extraneous substances such as surfactants and salting-out agents from the aggregates).

Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using a Nutsche method, 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 drier used in this step include a spray drier, a vacuum freeze drier, and a reduced-pressure drier, and a stationary shelf drier, a mobile shelf drier, a fluidized bed drier, a rotary drier. It is preferable to use a type dryer, a stirring type dryer and the like.

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

Incidentally, the dried toner particles are
In the case where the aggregates are aggregated by a weak attraction between particles, the aggregates may be crushed. Here, as the crushing device,
A mechanical pulverizer such as a jet mill, a Henschel mixer, a coffee mill, and a food processor can be used.

The toner of the present invention forms composite resin particles in the absence of a colorant, adds a colorant particle dispersion to the composite resin particle dispersion, and combines the composite resin particles with the colorant particles. It is preferably prepared by salting out / fusing.

As described above, by performing 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 fixing device is not stained or the image is not stained due to the accumulation of the toner.

Further, as a result of reliably performing the polymerization reaction for obtaining the composite resin particles, no monomer or oligomer remains in the obtained toner particles. No unpleasant odor is generated in the heat fixing step.

Further, the surface characteristics of the obtained toner particles are uniform and the charge amount distribution is sharp, so that an image having excellent sharpness can be formed for a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles, good adhesion (high fixing strength) to an image support is maintained in an image forming method including a fixing step by a contact heating method. Meanwhile, the offset resistance and the anti-winding property can be improved, and an image having an appropriate gloss can be obtained.

Next, each component used in the toner manufacturing process will be described in detail. (Polymerizable monomer) As a polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential component, and a crosslinkable monomer is optionally used. Used. As described below, at least one monomer having an acidic polar group or a monomer having a basic polar group is used.
It is desirable to contain a kind.

(1) Hydrophobic monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and a conventionally known monomer can be used. In addition, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics.

Specifically, monovinyl aromatic monomers,
It is possible to use (meth) acrylate monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers, and the like. it can.

Examples of the vinyl aromatic monomer include, for example,
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- Styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

The acrylic monomers include 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, propyl γ-aminoacrylate, stearyl methacrylate, methacryl Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like.

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

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

Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene and 4-methyl-1-pentene.

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. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

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

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

Examples of the (b) α, β-ethylenically unsaturated compound having a —SO ₃ H group include sulfonated styrene, its Na salt, allyl sulfosuccinic acid, allyl sulfosuccinate octyl, its Na salt and the like. be able to.

(4) Monomer having a basic polar group Examples of the monomer having a basic polar group include (i) an amine group or a quaternary ammonium group having 1 to 1 carbon atoms.
2, preferably 2 to 8, particularly preferably 2, (meth) acrylic esters of aliphatic alcohols, (ii) (meth)
Acrylamide or optionally N-C18
(Meth) acrylic acid amide mono- or di-substituted with an alkyl group, (iii) a vinyl compound substituted with a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-
Examples thereof include an alkylamine and a quaternary ammonium salt thereof. Among them, (i) the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferable as the monomer having a basic polar group.

Examples of (i) the (meth) acrylate of an aliphatic alcohol having an amine group or a quaternary ammonium group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, Quaternary ammonium salts of four compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
Examples thereof include 3-methacryloxypropyltrimethylammonium salt.

Examples of (ii) (meth) acrylamide or (meth) acrylamide optionally mono- or dialkyl-substituted on N include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, Methacrylamide, N-butyl methacrylamide, N, N-dimethylacrylamide,
N-octadecylacrylamide and the like can be mentioned.

Examples of the vinyl compound (iii) substituted with a heterocyclic group having N as a ring member include vinylpyridine,
Vinyl pyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like can be mentioned.

Examples of (iv) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride, N, N-diallylethylammonium chloride and the like.

(Polymerization Initiator) The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.), azo compounds (eg, 4,4 ′)
-Azobis-4-cyanovaleric acid and salts thereof, 2,2'-azobis (2-amidinopropane) salts and the like), peroxide compounds and the like. Further, the above radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. The use of a redox initiator is preferable because the polymerization activity is increased, the polymerization temperature can be reduced, and the polymerization time can be further shortened.

As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the minimum radical generation temperature of the polymerization initiator. For example, a temperature in the range of 50 ° C. to 90 ° C. is used. However, by using a polymerization initiator started at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (such as ascorbic acid), polymerization can be performed at room temperature or higher.

(Chain transfer agent: compound having a mercapto group) For the purpose of adjusting the molecular weight, a known chain transfer agent can be used. The chain transfer agent is not particularly limited, but a compound having a mercapto group is particularly preferably used because a toner having a sharp molecular weight distribution can be obtained, and storage stability, fixing strength, and offset resistance are excellent. . For example, compounds having a mercapto group such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, and the like,
Preferred are, for example, ethyl thioglycolate, propyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-thioglycolic acid.
Butyl, 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 pentaeristol, etc. Can be mentioned. Of these, n-octyl-3 is preferred from the viewpoint of suppressing odor during toner heat fixing.
-Mercaptopropionates are particularly preferred.

(Surfactant) In order to carry out the miniemulsion polymerization using the above-mentioned polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. Surfactants that can be used at this time are not particularly limited, but the following ionic surfactants can be mentioned as examples of suitable compounds.

Examples of the ionic surfactant include sulfonates (sodium dodecylbenzenesulfonate,
Sodium arylalkyl polyether sulfonate,
3,3-disulfonediphenylurea-4,4-diazo-
Sodium bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol -6
Sodium sulfonate), sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) are exemplified.

[0114] Nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, an ester of polyethylene glycol and higher fatty acid, an alkylphenol polyethylene oxide, an ester of higher fatty acid and polyethylene glycol, an ester of higher fatty acid and polypropylene oxide, And sorbitan esters.

In the present invention, these surfactants are mainly used as an emulsifier at the time of emulsion polymerization, but may be used for other steps or other purposes.

(Molecular Weight Distribution of Resin Particles and Toner) The toner of the present invention has a peak or shoulder of 100,000 to 1.0.
Preferably, the peak or shoulder is 100,000, and between 1,000 and 50,000.
000-1,000,000, 25,000-150,
More preferably it is present between 000 and 1,000 to 50,000.

The molecular weight of the resin particles is from 100,000 to
A resin containing at least a high molecular weight component having a peak or shoulder in the region of 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000 is preferred. More preferably, it is preferable to use an intermediate molecular weight resin having a peak or shoulder at a peak molecular weight of 15,000 to 100,000.

The method for measuring the molecular weight of toner or resin is as follows.
The measurement is preferably performed by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent. That is, 1.0 ml of THF is added to 0.5 to 5 mg, more specifically, 1 mg of a measurement sample, and the mixture is stirred at room temperature using a magnetic stirrer or the like to be sufficiently dissolved. Then, pore size 0.45 to 0.50
After treating with a μm membrane filter, the mixture is injected into GPC. The GPC measurement conditions were as follows: the column was stabilized at 40 ° C., THF was flowed at a flow rate of 1.0 ml per minute, and 1 m
Approximately 100 μl of a sample at a concentration of g / ml is injected and measured. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 802, 8 manufactured by Showa Denko KK
03, 804, 805, 806, 807, TSKgelG1000H, G2000H, manufactured by Tosoh Corporation,
G3000H, G4000H, G5000H, G600
0H, G7000H, TSKguard column
And the like. As the detector, a refractive index detector (IR detector) or a UV detector may be used. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodispersed polystyrene standard particles. As polystyrene for preparing a calibration curve, about 10 points may be used.

(Flocculant) The flocculant used in the present invention includes:
Those selected from metal salts are preferred.

Examples of the metal salt include salts of monovalent metals such as alkali metals such as sodium, potassium and lithium, salts of divalent metals such as alkaline earth metals such as calcium and magnesium, and salts of manganese and copper. Valent metal salts, iron,
Examples thereof include trivalent metal salts such as aluminum.

Specific examples of these metal salts are shown below.
Specific examples of metal salts of monovalent metals include sodium chloride,
Potassium chloride, lithium chloride, and metal salts of divalent metals include calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. In general, the divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt, and the trivalent metal salt has a smaller critical aggregation concentration.

The critical coagulation concentration referred to in the present invention is an index relating to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at which coagulation occurs when a coagulant is added. This critical aggregation concentration varies greatly depending on the latex itself and the dispersant. For example, Seizo Okamura et al., Polymer Chemistry 17,601
(1960), and according to these descriptions, the value can be known. Also, as another method,
It is also possible to add a desired salt to the target particle dispersion at a different concentration, measure the ζ potential of the dispersion, and determine the salt concentration at the point where the ζ potential changes to be the critical aggregation concentration.

In the present invention, the polymer fine particle dispersion is treated using a metal salt so as to have a concentration higher than the critical aggregation concentration. At this time, of course, add the metal salt directly,
The addition as an aqueous solution is arbitrarily selected depending on the purpose. In the case of adding as an aqueous solution, the added metal salt needs to be at or above the critical aggregation concentration of the polymer particles 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 as the coagulant in the present invention may be at least the critical coagulation concentration, but is preferably added at least 1.2 times, more preferably at least 1.5 times the critical coagulation concentration.

(Colorant) The toner of the present invention is obtained by salting out / fusing the composite resin particles and the colorant particles.

Examples of the colorant (colorant particles subjected to salting out / fusion with the composite resin particles) constituting the toner of the present invention include various inorganic pigments, organic pigments, and dyes. Conventionally known inorganic pigments 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. The amount of the pigment to be 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-mentioned magnetite can be added. In this case, from the viewpoint of imparting predetermined magnetic characteristics, 20 to 6
It is preferable to add 0% by mass.

Conventionally known organic pigments and dyes can also be used. Specific examples of organic pigments and dyes are shown below.

The pigments for magenta or red include:
For example, C.I. 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. Pigment Red 15, C.I. I. Pigment Red 16, C.I. 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. I. Pigment red 144, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 1
66, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222
And the like.

Examples of orange or yellow pigments include C.I. I. Pigment Orange 31, C.I.
I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. 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 9
4, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 1
85, C.I. I. Pigment yellow 155, C.I. I. Pigment Yellow 156 and the like.

Examples of green or cyan pigments include:
For example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

As the dye, for example, C.I. I. Solvent Red 1, 49, 52, 58, 63
111, 122, C.I. I. Solvent Yellow 1
9, 44, 77, 79, 81, 82, 9
3, 98, 103, 104, 112, 16
2, C.I. I. Solvent Blue 25, 36, 60
70, 93, 95, etc., and mixtures thereof can also be used.

These organic pigments and dyes can be used alone or in combination as required.
The amount of the pigment added is 2 to 20% by mass based on the polymer.
And preferably 3 to 15% by mass.

The colorant (colorant particles) constituting the toner of the present invention may be surface-modified. As the surface modifier, a conventionally known one 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 the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, and vinyltrimethoxysilane. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane and the like. As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 138, which are commercially available under the trade name of “Preneact” manufactured by Ajinomoto Co., Inc.
S-1, 238S, etc., commercial products A-1 and B- manufactured by Nippon Soda Co., Ltd.
1, TOT, TST, TAA, TAT, TLA, TO
G, TBSTA, A-10, TBT, B-2, B-4,
B-7, B-10, TBSTA-400, TTS, TO
A-30, TSDMA, TTAB, TTOP and the like. As the aluminum coupling agent, for example,
"Plenact AL-M" manufactured by Ajinomoto Co. and the like.

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

As a method for modifying the surface of the colorant particles, there is a method in which a surface modifier is added to a dispersion of the colorant particles, and the system is heated and reacted.

[0139] The surface-modified colorant particles are collected by filtration, and dried and washed after repeated washing and filtering with the same solvent.

(Releasing Agent) The toner used in the present invention comprises:
It is preferable that the toner is obtained by fusing resin particles containing a release agent in an aqueous medium. In this manner, the resin particles in which the release agent is encapsulated in the resin particles are salted out / fused with the colorant particles in an aqueous medium, whereby a toner in which the release agent is finely dispersed can be obtained.

In the toner of the present invention, a low molecular weight polypropylene (number average molecular weight = 1500 to 900) is used as a releasing agent.
0), low molecular weight polyethylene, and the like are preferable, and an ester compound represented by the following formula is particularly preferable.

R ^1- (OCO-R ² ) _{n In the} formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4. R ¹ , R
² represents a hydrocarbon group which may have a substituent. R ¹
Has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ² has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

Next, examples of typical compounds are shown below.

[0144]

Embedded image

[0145]

Embedded image

The addition amount of the above compound is 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 15% by mass based on the whole toner.

The toner of the present invention is preferably prepared by encapsulating the above-mentioned release agent in resin particles by miniemulsion polymerization, salting out and fusing with the toner particles.

(Charge Control Agent) In addition to the colorant and the release agent, a material capable of imparting various functions as a toner material can be added to the toner. Specific examples include a charge control agent. These components can be added simultaneously with the resin particles and the colorant particles in the above-mentioned salting-out / fusion step, and can be added by various methods such as a method of including in the toner and a method of adding to the resin particles themselves.

As the charge control agent, various known charge control agents which can be dispersed in water can be used. Specific examples include 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 metal salt of salicylic acid, and a metal complex thereof.

(External Additive) A so-called external additive can be added to the toner of the present invention for the purpose of improving fluidity and cleaning properties. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles, and lubricants can be used.

As the inorganic fine particles that can be used as the external additive, conventionally known inorganic fine particles can be exemplified. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

As specific examples of the silica fine particles, commercially available products R-805, R-976, and R-980 manufactured by Nippon Aerosil Co., Ltd.
974, R-972, R-812, R-809, HVK-2150 and 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 and the like.

Specific examples of the titanium fine particles include, for example,
Commercial products T-805 and T-60 manufactured by Nippon Aerosil Co., Ltd.
4. Commercial products MT-100S and 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, and commercial products IT-S, IT-OA, IT-OB, IT-OC manufactured by Idemitsu Kosan Co., Ltd.

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

Examples of the 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 the organic fine particles include polystyrene, polymethyl methacrylate, and styrene-methyl methacrylate copolymer.

Examples of the lubricant which 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 metal stearate salts such as zinc stearate, aluminum stearate, copper stearate, magnesium stearate, and calcium stearate; zinc oleate, manganese oleate, iron oleate, and olein. Metal salts of oleic acid such as copper phosphate and magnesium oleate; Metal salts of palmitic acid such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; Metal salts of linoleic acid such as zinc linoleate and calcium linoleate; Ricinol And metal salts of ricinoleic acid such as zinc acid and calcium ricinoleate.

The addition amount of the external additive is preferably about 0.1 to 5% by mass based on the toner.

<Step of Adding External Additive> This step is a step of adding an external additive to the dried toner particles.

Examples of the device used for adding the external additive include a turbular mixer, a Hensiel mixer,
Various known mixing devices such as a Nauta mixer and a V-type mixer can be used.

(Toner Particles) The particle size of the toner of the present invention is as follows.
The number average particle diameter is preferably from 3 to 10 μm, more preferably from 3 to 8 μm. This particle size can be controlled by the concentration of the coagulant (salting agent), the amount of the organic solvent added, the fusing time, and the composition of the polymer in the method for producing the toner.

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

The number average particle diameter of the toner is determined by using a Coulter Counter TA-II, Coulter Multisizer, SLAD
It can be measured using 1100 (a laser diffraction particle size analyzer manufactured by Shimadzu Corporation) or the like.

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

<Preferable Shape Factor Range of Toner Particles>
The shape factor of the toner of the present invention is 1.0% to 1.6% by number, preferably 65% by number or more, and preferably 1.2% to 1.6%.
More than 5% by number, particularly preferably 1.2 to 1.6 is 70% by number or more.

The shape factor of the toner of the present invention is represented by the following equation, and indicates the degree of roundness of toner particles.

Shape coefficient = ((maximum diameter / 2) 2 × π) / projected area Here, the maximum diameter is defined as the parallel image when the projected image of the toner particles on the plane is sandwiched between two parallel lines. Means the width of the particle at which the distance between the particles becomes maximum. The projection area refers to the area of the projected image of the toner particles on the plane. In the present invention, the shape factor can be determined by taking a photograph in which the toner particles are magnified 2,000 times with a scanning electron microscope, and then referring to the “SCCANNING IMAGE ANALYZE” based on the photograph.
R "(manufactured by JEOL Ltd.) was used to analyze photographic images. In this case, the shape factor of the present invention was measured by using the above formula using 100 toner particles.

In the toner of the present invention, when the particle diameter of the toner particles is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution, the sum (M1) of the relative frequency (m1) of the toner particles included in the most frequent class and the relative frequency (m2) of the toner particles included in the class having the second highest frequency after the 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 narrower. Thus, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution is obtained by plotting 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 to 2.07: 2.07 to 2.30: 2.30 to
2.53: 2.53 to 2.76...) Is a histogram showing the number-based particle size distribution, which is a 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 the computer creates the program using a particle size distribution analysis program.

[Measurement conditions] 1: Aperture: 100 μm 2: Sample preparation method: Electrolyte [ISOTON R-11
(Coulter Scientific Japan) 5
An appropriate amount of a surfactant (neutral detergent) is added to 0 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 a dispersion treatment with an ultrasonic disperser for 1 minute.

(Developer) 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, a non-magnetic one-component developer or 0.1 to 0.5 μm
And a magnetic one-component developer containing a certain amount of magnetic particles, and any of them can be used.

Further, it can be used as a two-component developer by mixing with a carrier. In this case, as magnetic particles of the carrier, 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. Particularly, ferrite particles are preferable. The magnetic particles have a volume average particle size of 15 to 100 μm, more preferably 25 to 8 μm.
It is preferably 0 μm.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)
(ATEC)).

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

(Image Forming Method) The toner of the present invention includes an image fixing step in which an image forming support having a toner image formed thereon is passed between a heating roller and a pressure roller constituting a fixing device and fixed. Forming method (image forming method of the present invention)
It is preferably used.

FIG. 1 is a cross-sectional view showing an example of a fixing device used in the image forming method using the toner of the present invention. The fixing device shown in FIG. And a roller 20. In FIG. 1, 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 body formed on the surface of a metal core 11, and includes 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 constituting the metal core 11 is not particularly limited, but examples thereof include metals such as iron, aluminum and copper or alloys thereof.

The thickness of the core metal 11 is set to 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 to maintain a strength equivalent to that of a 0.57 mm iron core with an aluminum core, the wall thickness must be 0.8 mm.

As the fluororesin constituting the coating layer 12, PTFE (polytetrafluoroethylene) and P
FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) and the like can be exemplified.

The coating layer 12 made of fluororesin has a thickness of 1
It is 0-500 μm, preferably 20-400 μm.

When the thickness of the coating layer 12 made of fluororesin is 1
When the thickness is less than 0 μm, the function as a coating layer cannot be sufficiently exhibited, and the durability as a fixing device cannot be secured. On the other hand, there is a problem 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, thereby causing image stains.

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

Elastic Asker C constituting the coating layer 12
The hardness is less than 80 °, preferably less than 60 °.

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

Elastic Asker C constituting the coating layer 12
When the hardness exceeds 80 ° and when the thickness of the coating layer 12 is less than 0.1 mm, the nip for fixing cannot be increased, and the effect of soft fixing (for example, the smoothed interface Improvement effect of color reproducibility by toner layer)
Cannot be demonstrated.

As the heating member 13, a halogen heater can be suitably used. The pressure roller 20
A coating layer 22 made of an elastic body is formed on the surface of the core metal 21. The elastic body constituting the coating layer 22 is not particularly limited, and examples thereof include various soft rubbers such as urethane rubber and silicone rubber and sponge rubber, and the silicone rubber exemplified as the material constituting the coating layer 12 and the like. It is preferable to use silicone sponge rubber.

Elastic Asker C constituting the coating layer 22
The hardness is less than 80 °, preferably less than 70 °, more preferably less than 60 °.

The thickness of the coating layer 22 is 0.1 to 30 m.
m, and preferably 0.1 to 20 mm.

Elastic Asker C constituting the coating layer 22
When the hardness exceeds 80 ° and when the thickness of the coating layer 22 is less than 0.1 mm, the nip for fixing cannot be increased, and the effect of soft fixing cannot be exhibited.

The material constituting the core metal 21 is not particularly limited, but examples thereof include metals such as aluminum, iron, and copper or 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, more preferably 50 to 300 N.
２５０250N. This contact load is applied to the heating roller 1
It is defined in consideration of the strength of 0 (the thickness of the core 11). For example, in a heating roller having a core of 0.3 mm made of iron, the heating roller is preferably set to 250 N or less.

From the viewpoints of offset resistance and fixability, the nip width is preferably 4 to 10 mm, and the nip has a surface pressure of 0.6 × 10 5 Pa to 1.0.
It is preferably 5 × 105 Pa.

One example of the fixing conditions by the fixing device shown in FIG. 1 is as follows: fixing temperature (surface temperature of heating roller 10).
Is 150 to 210 ° C., and the fixing linear velocity is 80 to 640 m.
m / sec.

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

As the silicone oil, those having high heat resistance are used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone and the like are used. Since those having a low viscosity have a large outflow during 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 remarkably exhibited when an image is formed by using a fixing device that does not supply silicone oil or that supplies a very small amount of silicone oil. Therefore, even when the silicone oil is supplied, the supply amount is preferably 2 mg or less per A4 sheet.

By setting the supply amount of the silicone oil to 2 mg or less per A4 sheet, the amount of the silicone oil adhering to the transfer paper (image support) after fixing is reduced, and the ballpoint pen is formed by the silicone oil adhering to the transfer paper. There is no difficulty in writing with an oil-based pen, etc., and the writing performance is not impaired.

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

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

[0202]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples.

<< Preparation of Various Deodorants >> Deodorants 1 to 11 were prepared according to the following method.

<Deodorant 1: Deodorant of Plant Extract Component> 10 g of F118 (manufactured by Fine 2), which is a commercially available deodorant of plant extract component, was dissolved in 2 kg of ion-exchanged water at 40 ° C. Deodorant 1 was prepared.

<Deodorant 2: Deodorant containing phytoncide as a plant extractable component> BioDash D-200 (manufactured by Daiso), which is a commercially available deodorant of a plant extractable component
g was dissolved in 2 kg of ion exchanged water at 40 ° C. to prepare a deodorant 2.

<Deodorant 3: Deodorant containing catechin and flavonoid as plant extract components> 50 g of fresh leaves of tea leaves
Is ground to a particle size of 1 mm or less.
The ethanol extract 1 extracted with 200 ml of a 50% aqueous ethanol solution at a temperature of 2% has an active ingredient content of 2% by mass.
And the ethanol content was 50% by mass and the water content was 48% by mass. Table 1 shows the composition (unit% by mass) of the active ingredient contained in the ethanol extract 1 prepared above.

[0207]

[Table 1]

Next, as a plant having a high content of flavonoids, sprouts and immature apples were used to extract ethanol extract 2
Was prepared. Specifically, 30 g of sprouts, 50 immature apples
g was immersed in 100 ml of water to extract a plant extract. 200 ml of the ethanol extract 1 was added to 100 ml of the plant extract obtained by this extraction, and the plant extract was blended to obtain an ethanol extract 2 containing catechin and flavonoid. In the ethanol extract 2, the active ingredient was 6% by mass, and the ethanol content was 36% by mass.
And the water content was 58% by mass. This ethanol extract 2 was dissolved in 2 kg of ion-exchanged water at 40 ° C. to prepare a deodorant solution. The obtained deodorant liquid was used as deodorant 3.

<Deodorant 4: Enzymatic Deodorant> A commercially available deodorant, Biodash P-500 (manufactured by Daiso) 5
g was dissolved in 2 kg of ion exchanged water at 40 ° C. to prepare a deodorant 4.

<Deodorant 5: Enzymatic Deodorant Containing Plant Extract Component> 5 g of Bio-C (an enzyme deodorant manufactured by Consol Corporation and containing a plant extract component) which is a commercially available deodorant Was dissolved in 2 kg of ion-exchanged water at 40 ° C. to prepare a deodorant 5.

<Deodorant Liquid 6: Metal Phthalocyanine Deodorant> 1% by mass of octacarboxyphthalocyanine iron was dissolved in an alkaline aqueous solution to prepare a deodorant liquid 6.

<Deodorant 7: Artificial enzyme deodorant> 10 g of β-cyclodextrin and 25 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride were mixed and reacted under the conditions of pH 9.0 and 70 ° C. A cationic group was introduced into β-cyclodextrin. Next, 3 g of octacarboxyl iron phthalocyanine was dissolved in 100 ml of a 0.1% aqueous sodium hydroxide solution, and the pH was adjusted with acetic acid.
After adjusting the pH to 8.0, β
-After adding cyclodextrin and mixing uniformly, 90
C., and reacted for 60 minutes to prepare a target artificial enzyme solution. Deodorant 7 was prepared by diluting 100 ml of the obtained artificial enzyme solution with 2 kg of ion-exchanged water.

<Deodorant 8: Microbial Deodorant 1> Ammonium chloride 0.5 g Glucose 5.0 g Water 2.5 L Microbial powder: Bacillus subtilis 5.0 g was mixed and stirred at 30 ° C. for 24 hours. This culture was centrifuged, and the resulting supernatant was used as deodorant 8.

<Deodorant 9: Microbial Deodorant 2> A culture solution was prepared in the same manner as in the preparation of the deodorant 8, except that a mixture of Bacillus subtilis and Streptococcus facaris was used as the microbial powder. Then, the culture was centrifuged to obtain a supernatant. Furthermore, the supernatant 15
To 0 ml, add and mix 100 g of glutaraldehyde, dilute to 2 liters with ion-exchanged water,
Was prepared.

<Deodorant 10: Deodorant Immobilized on Nonwoven Fabric> The artificial enzyme solution prepared with the deodorant 7 was immersed in a breathable nonwoven fabric, and the nonwoven fabric was dried to prepare the deodorant 10. did.

<Deodorant 11: Deodorant having microorganisms fixed to porous powder> A deodorant 11 was prepared using the following microorganisms I to IV, saccharides, a water-soluble nitrogen compound, and porous powder. .

Microorganism I: B. subtilis Microorganism II: Enterobacter (E. sakazak)
i) Microorganism III: genus SRA (S. faecalis,
R. oryzae, A .; niger) Microorganism IV: genus NNP (N. europaea, N. niger)
Agilis, P.A. Carryophili Saccharide: glucose Water-soluble nitrogen compound: ammonium chloride Porous powder: larch pine sawdust (particle size 0.1 to 2 by sieve)
mm: 0% for 45 μm or less) Water: ion-exchanged water 5 g of each of the microorganisms I to IV is put into a jar fermenter together with 7 g of glucose, 0.7 g of ammonium chloride, 40 g of sawdust and 1500 g of water, and the temperature is 30 ° C. After culturing for 24 hours at an oxygen aeration rate of 0.05 L / min, freeze-drying was carried out to prepare a deodorant 11 containing microorganisms I to IV fixed on a porous powder.

<< Preparation of Toner and Developer >> (Preparation of Latex) [Preparation of Latex 1HML] <1: Preparation of Nuclear Particles (First Stage Polymerization)> A stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device were installed. 5000m
In a separate separable flask, add an anionic surfactant A
_{(C 10 H 21 (OCH 2} CH 2) 2 OSO 4 Na) 7.08g
Was dissolved in 3010 g of ion-exchanged water, and an inner temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm in a nitrogen stream.

To this surfactant solution was added 9.2 g of a polymerization initiator (potassium persulfate: KPS) in 200 g of ion-exchanged water.
Was added, and the temperature was adjusted to 75 ° C., and then 70.1 g of styrene and n-butyl acrylate 1 were added.
A monomer mixture composed of 9.9 g and 10.9 g of methacrylic acid was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours to perform polymerization (first-stage polymerization). Latex (a dispersion of resin particles composed of a high molecular weight resin) was prepared. This is designated as latex 1H.

<2: Formation of Intermediate Layer (Second Stage Polymerization)> In a flask equipped with a stirrer, styrene 10
To a monomer mixture consisting of 5.6 g, 30.0 g of n-butyl acrylate, 6.4 g of methacrylic acid, and 5.6 g of n-octyl-3-mercaptopropionate, was added Example Compound 19 as a release agent. 0 g was added, and the mixture was heated and dissolved at 80 ° C. to prepare a monomer solution 1. Next, 1.6 g of the anionic surfactant A was added to ion-exchanged water 27.
Heat the surfactant solution dissolved in 00 ml to 80 ° C.
To this surfactant solution, 28 g of the latex 1H, which is a dispersion of core particles, was added in an amount of 28 g in terms of solid content, and then a mechanical disperser “CLEARMIX (CLEARM) having a circulation path was used.
IX) ”(manufactured by M Technique Co., Ltd.), and the above-prepared monomer solution 1 was mixed and dispersed to prepare an emulsion containing emulsified particles having a uniform dispersed particle diameter (284 nm).

Next, a polymerization initiator (KP
S) Polymerization (second-stage polymerization) was carried out by adding an initiator solution obtained by dissolving 5.1 g in 240 ml of ion-exchanged water and 750 ml of ion-exchanged water, and heating and stirring this system at 80 ° C. for 3 hours. And a latex (a dispersion 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). This is referred to as latex (1HM).

<3: Formation of outer layer (third stage polymerization)> A polymerization initiator (KPS) was added to the latex 1HM prepared above.
An initiator solution obtained by dissolving 4 g in 200 ml of ion-exchanged water was added, and 300 g of styrene was added under a temperature condition of 80 ° C.
-95 g of butyl acrylate, 15.3 of methacrylic acid
g, a monomer mixture consisting of 10.4 g of n-octyl-3-mercaptopropionate was added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) is carried out by heating and stirring for 2 hours, then cooled to 28 ° C., and a latex (a central portion composed of a high molecular weight resin, an intermediate layer composed of an intermediate molecular weight resin, A dispersion of composite resin particles having an outer layer made of a low-molecular-weight resin and having the intermediate layer containing Exemplified Compound 19 as a release agent was obtained. This latex is referred to as latex 1HML.

The composite resin particles constituting the latex 1HML were 138,000, 80,000 and 13,
It had a peak molecular weight of 000, and the composite resin particles had a mass average particle size of 122 nm.

[Preparation of latex 2HML] In the preparation of latex 1HML, anionic surfactant A
In place of anionic surfactant B (sodium dodecyl sulfonate: SDS), except that
Latex (a dispersion of composite resin particles having a central portion composed of a high molecular weight resin, an intermediate layer composed of an intermediate molecular weight resin, and an outer layer composed of a low molecular weight resin) was obtained. This latex is referred to as latex 2HML.

The composite resin particles constituting the latex 2HML were 138,000, 80,000 and 12,000.
The composite resin particles had a peak molecular weight of 000, and the mass average particle size of the composite resin particles was 110 nm.

(Preparation of Toner) [Preparation of Toner Particles] <Preparation of Toner Particles 1 to 9> 59.0 g of anionic surfactant A and 1600 ml of ion-exchanged water were stirred and dissolved. While stirring this solution, 420.0 g of carbon black “REGAL 330” (manufactured by Cabot) is gradually added, and then the mixture is dispersed by using “CLEARMIX” (manufactured by M Technic) to be colored. A dispersion of agent particles (hereinafter, referred to as a colorant dispersion 1) was prepared. When the particle size of the colorant particles in this colorant dispersion 1 was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the mass average particle size was 9%.
It was 8 nm.

The prepared latex 1HML was added to 42
0.7g (solid content conversion) and 900g of ion exchange water
And 166 g of Colorant Dispersion Liquid 1 were placed in a reaction vessel (four-neck flask) equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device, and stirred. After adjusting the internal temperature to 30 ° C., a 5 mol / L aqueous sodium hydroxide solution was added to the solution to adjust the pH to 11.0.

Subsequently, magnesium chloride hexahydrate12.
An aqueous solution obtained by dissolving 1 g in 1000 ml of ion-exchanged water,
It was added over 30 minutes at 30 ° C. under stirring. After standing for 3 minutes, the temperature was raised, and the aqueous solution was added to the solution over 6 minutes.
The temperature was raised to 0 ° C (heating rate: 10 ° C / min). In this state, the particle size of the associated particles was measured with a “Coulter counter TA-II”, and when the number average particle size became 5.5 μm, 80.4 g of sodium chloride was added to ion-exchanged water 1000.
stop the particle growth by adding an aqueous solution dissolved in ml,
Further, fusion was continued by heating and stirring at a liquid temperature of 85 ° C. for 2 hours as an aging treatment. afterwards,
Cool to 30 ° C at 8 ° C / min, add hydrochloric acid and add p
H was adjusted to 2.0 and stirring was stopped. The generated associated particles are filtered with Nutsche, washed repeatedly with 45 ° C. ion-exchanged water, and the above prepared deodorants 1 to 9 are poured onto Nutsche, filtered, and dried with warm air at 40 ° C. In this way, toner particles 1 to 9 of the present invention having the configurations shown in Table 2 below were prepared.

<Preparation of Comparative Toner Particles 1> Next, comparative toner particles 1 were prepared in the same manner as in the preparation of the toner particles 1 to 9 except that the deodorant treatment was not performed.

<Preparation of Toner Particles 10> In the preparation of the toner particles 1 to 9, 420.7 g (in terms of solid content) of the prepared latex 1HML was mixed with ion-exchanged water 90%.
After adding 0 g, stirring was performed for 30 minutes by a device in which a deodorant 10 (a deodorant fixed to the nonwoven fabric) was fixed to a stirring spring,
Toner particles 10 were prepared in the same manner except that Colorant Dispersion 1 was added.

<Preparation of Toner Particles 11> In the preparation of the toner particles 1 to 9, 420.7 g (in terms of solid content) of the prepared latex 1HML was added to ion-exchanged water 90%.
After adding 0 g, deodorant 11 (porous deodorant) was added, and the mixture was stirred for 30 minutes. After removing the deodorant with a 350 mesh filter, the same procedure was performed except that colorant dispersion 1 was added. Thus, toner particles 11 were prepared.

[Preparation of Developer] Hydrophobic silica (number-average primary particle diameter = 10 nm, degree of hydrophobicity = 63) was added to the above-prepared toner particles 1 to 11 and comparative toner particle 1 in an amount of 1.0%.
%, And hydrophobic titanium oxide (number average primary particle size = 25 nm, degree of hydrophobicity = 60) was added at a ratio of 1.2% by mass, respectively, and mixed with a Henschel mixer. Each of toner particles to which hydrophobic silica and hydrophobic titanium oxide are added, and a ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm are mixed. Developer 1 was prepared.

<< Evaluation of Characteristics >> Each characteristic was evaluated according to the following method.

[Evaluation of Toner Storage Property]
After leaving for 18 hours in an environment of 5 ° C. and a relative humidity of 90% RH, the mixture was passed through a 100-mesh sieve, and the granules on the sieve were 0.1 g.
The following items were evaluated as “◎”, those with 0.1 to 0.3 g as “○”, and those with 0.3 g or more as “×”, and the preservability of toner particle size under a high temperature and high humidity environment was evaluated.

[Evaluation of Fixing Rate] The fixing rate was determined using a commercially available digital copying machine “Konica Sitios 7075” (manufactured by Konica Corporation) as an evaluator, and the toner adhesion amount was 0.6 mg / cm ² of 2.54 cm. A (1 inch) square solid image was collected, Scotch mending tape (manufactured by Sumitomo 3M) was stuck on the solid image surface, the tape was peeled off, and the image density before and after peeling was measured. The fixing rate was evaluated.

Fixing rate = Image density after peeling / Image density before peeling × 100 [%] In the above evaluation, if the fixing rate was 80% or more, it was judged that the performance was practically acceptable.

[Odor Test by Practical Technique] Each toner was attached to the above digital copier “Konica Sitios 7075” from which an exhaust filter was removed, and a continuous chart of 7% of the image area was printed on 1,000 sheets. The odor was determined by 20 general panelists according to the following criteria.

◎: Almost no odor was observed. ：: Slight odor was observed, but no discomfort was found. X: Discomfort odor was observed. [Evaluation of Environment Dependency of Charging] Konica Sitios 7075 ”was used as an evaluator, and a low-temperature and low-humidity environment (10 ° C., 20% RH) and a high-temperature and high-humidity environment (33
At 80 ° C., 80% RH).
The charge amount of each developer under each environment was measured by a blow-off method, and was determined according to the following criteria.

：: Difference of less than 3 μC / g ○: Difference of 3 μC / g or more and less than 6 μC / g Δ: Difference of 6 μC / g or more and less than 9 μC / g ×: Difference of 9 μC / g or more It was judged that there was no practical problem within the range.

Table 2 shows the results obtained by the above evaluations.

[0241]

[Table 2]

As is clear from Table 2, the toner using the toner particles containing the deodorant according to the present invention has almost no odor and has a lower temperature and a higher humidity than the comparative example. It can be seen that this is excellent in storage stability, fixability and change in charge amount due to environmental change.

[0243]

According to the present invention, in a normal toner manufacturing method, a very small amount of odorous substances generated by the decomposition of a part of toner components due to a very small amount of odorous substances and a storage environment at the time of manufacturing can be effectively removed. The present invention can provide a toner and a method for producing the toner, which are deodorized and removed, have a small odor of the toner itself and a low odor during fixing, and are excellent in the preservability, fixing property and chargeability of the toner.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a fixing device used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 heating roller 11, 21 core metal 12, 22 coating layer 13 heating member 20 pressure roller T toner image formed on transfer paper (image forming support)

Claims (14)

[Claims] 1. A method in which a resin formed by polymerizing at least a polymerizable monomer in an aqueous medium and a toner particle containing a colorant are separated from the aqueous medium by a deodorant containing a plant extract component before the toner particles are separated from the aqueous medium. A method for producing a toner. 2. The method according to claim 1, wherein at least one of the plant extract components comprises:
2. The method according to claim 1, wherein the toner is a phytontide. 3. The method according to claim 1, wherein at least one of the plant extract components comprises:
The method according to claim 1, wherein the toner is a catechin. 4. A method in which at least a resin formed by polymerizing a polymerizable monomer in an aqueous medium and toner particles containing a colorant are treated with an enzyme-containing deodorant before separation from the aqueous medium. A method for producing a toner, comprising: 5. A method in which at least a resin formed by polymerizing a polymerizable monomer in an aqueous medium and toner particles containing a colorant are treated with a metal phthalocyanine-based deodorant before separation from the aqueous medium. A method for producing a toner. 6. An artificial enzyme deodorant containing metal phthalocyanines before separating toner particles containing a resin and a colorant formed by polymerizing at least a polymerizable monomer in an aqueous medium from the aqueous medium. And a method for producing a toner. 7. A method in which a resin formed by polymerizing at least a polymerizable monomer in an aqueous medium and a toner particle containing a colorant are treated with a microbial deodorant before being separated from the aqueous medium. Toner production method. 8. A deodorant liquid which is dissolved or dispersed in water before separating a resin and a colorant-containing toner particle formed by polymerizing at least a polymerizable monomer in an aqueous medium from the aqueous medium. And a method for producing a toner. 9. A porous powder or nonwoven fabric having a deodorant fixed thereon before separating toner particles containing a resin and a resin formed by polymerizing at least a polymerizable monomer in an aqueous medium from the aqueous medium. And a method for producing a toner. 10. A method for polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group, wherein a resin extract and a colorant are contained on the surface of toner particles, and a plant extract component is contained on the surface of the toner particles. A toner characterized in that a deodorant is absorbed. 11. A method for polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group, and forming an enzyme containing enzyme on the surface of toner particles containing a resin and a colorant. A toner characterized by adsorbing an odorant. 12. A metal phthalocyanine-based deodorant is applied to the surface of toner particles containing a resin and a colorant formed through a step of polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group. A toner characterized by adsorbing an agent. 13. A method for polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group, wherein a metal phthalocyanine is contained on the surface of toner particles containing a resin and a colorant. A toner characterized in that an artificial enzyme deodorant is absorbed. 14. A microbial deodorant on the surface of toner particles containing a resin and a colorant formed through a step of polymerizing at least a polymerizable monomer in an aqueous medium in the presence of a compound having a mercapto group. A toner characterized in that the toner is absorbed.