JP2003173041A - Electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic device using toner that gives off smell pleasant to a human being (aroma) and improves job efficiency, by designing such that smell emitted by an electrophotographic device such as a copying machine or printer, which has become more widespread, use is correctly evaluated. <P>SOLUTION: The electrophotographic device has an image carrier on the surface of which an electrostatic latent image is formed by an electrostatic potential difference and a developing device which forms a toner image by depositing toner to the electrostatic latent image, and fixes the toner image, transferred to the surface of a recording sheet, under heat and pressure. In the electrophotographic image device, the toner is produced through the step of forming particles within a water-system medium, the step of processing an aroma chemical, and the step of drying. As the toner mass of 4 to 158 g is fixed per minute. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to copiers, printers, facsimiles, etc. to form an electrostatic latent image on an image bearing member and develop the formed electrostatic latent image with toner to form an image. The present invention relates to an electrophotographic device.

[0002]

2. Description of the Related Art Impurities contained in a toner for electrostatic latent image development (hereinafter sometimes simply referred to as toner) used in electrophotography and the like, particularly components having a low molecular weight odor, are However, when the toner container is opened, it may cause a problem such as giving off an odor that gives an unpleasant feeling.

Further, as a method of fixing the toner image on the copy paper surface, a heat fixing method or the like is usually used. Further, as the heat fixing method, generally, a heating roller fixing method and an endless belt fixing method are widely used. These methods are extremely effective as a fixing method because they have very good thermal efficiency when fusing a toner image to be fixed onto a transfer material and can fix them quickly.

However, in these methods, the toner image is heated and fixed, and particularly when the endless belt fixing method in which the contact heating time (fixing nip portion passage time) is long in the heat fixing section is used, Trace components contained in the toner may be released into the atmosphere, which may cause an unpleasant odor for the user. Further, in recent years, with the downsizing of copiers and printers, there are more and more opportunities to use them in offices and the like. In addition, the chances of using it in general households are increasing, and as a result, the odor emitted from the toner is often more unpleasant to the user than ever before. On the other hand, there is a growing interest in odors socially, and those that produce a good odor (aroma) are welcomed, but conversely, those that produce a bad odor tend to be extremely avoided.

As a cause of the bad odor generated from the electrophotographic apparatus, ozone is generated by corona discharge, but a technical innovation of a contact charging method such as roller charging or brush charging, or a corona discharger in which ozone generation is suppressed as much as possible. As a result, the ozone odor was dramatically reduced, and the toner odor caused by the toner was relatively unpleasant in many cases.

As a preventive measure against this, there is a case where a filter or the like for adsorbing an odor is attached to the main body device, but these are disadvantageous in terms of production cost, and in order to maintain the deodorizing function, There is also the annoyance of regular replacement.

As a method for reducing the odor derived from the toner, there is a conventional method for reducing impurities in the binder resin (binder resin). For example, Japanese Patent Laid-Open No. 64-707
No. 65, No. 64-88556, and JP-A-8-3.
Japanese Patent No. 28311 proposes reduction of odor by reducing residual monomers in the binder resin. Also,
In JP-A-7-104515, JP-A-7-104514, etc., it is considered that it is not enough to reduce the volatile components contained in the resin. Since a volatile substance generated by decomposing a stable substance causes generation of an odor, a technique for removing the odor of the raw material is disclosed.

Further, Japanese Patent Laid-Open No. 8-171234 discloses an oxidation product of benzaldehyde contained in a toner as a substance causing odor, and attempts to reduce the content of benzaldehyde. On the other hand, in Japanese Unexamined Patent Publication No. 9-230628, the odor is improved by reducing the amount of the alkyl mercaptan used as a molecular weight control agent for the resin, which is essential for the basic performance of the toner, and suppressing it to the necessary minimum amount. At the same time, the device is devised to prevent the fixing property from being adversely affected.

Further, JP-A-3-105350 discloses an attempt to add an alkyl betaine compound to a toner as a substance that reacts with or adsorbs an odor substance. Furthermore, JP-A-2-240663 describes a method of deodorizing by contacting a deodorant and a toner for 5 hours or more in a pulverizing and classifying process, but this method requires a long manufacturing time and The odor generated after the end of manufacturing is not reduced.

[0010]

In any of the above methods,
Since the content of odorous substances that humans can perceive is extremely small, it is difficult to take measures against it.

However, another important point is that human perception of odor is delicate, and it is difficult to judge whether it is a good odor (fragrance) or a bad odor, and it is odorless. It is necessary to look at this problem from the perspective of whether humans feel comfortable in a state.

From this point of view, a technique for accurately evaluating and designing the quality of the odor generated by an extremely small amount of inclusion based on an objective standard, and based on that, what kind of odor is produced Need to know if he feels comfortable.

That is, the object of the present invention is to accurately evaluate and design the odor produced by electrophotographic devices such as copying machines and printers, which have become more and more popular recently, and to produce a odor (aroma) that is comfortable for humans. I will issue it. Further, since the electrostatic latent image developing toner is the largest cause of the odor emitted by the electrophotographic apparatus, it is possible to evaluate and design the toner from the viewpoint of producing a pleasant odor during image formation in advance. To do.

[0014]

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

1. An image bearing member on the surface of which an electrostatic latent image due to an electrostatic potential difference is formed, and a developing device for adhering toner to the electrostatic latent image to form a toner image, are transferred onto a recording sheet. An electrophotographic apparatus for fixing a toner image by heating and pressurizing the toner image is produced through a step of forming particles in an aqueous medium, a perfume processing step and a drying step, and the toner mass is 4 to 158 g / min. An electrophotographic device, characterized in that it fixes the.

2. In the odor space formed by styrene and n-butyl acrylate, the toner has a cos θ of 0.990 to 0.998 for styrene odor and a cos θ of 0.986 to 0.
2. The electrophotographic apparatus as described in the above item 1, wherein the electrophotographic apparatus is 994 and has a strength of 1.8 to 2.6.

3. The toner has a cos θ of 0.990 to 0.998 with respect to a styrene odor in an odor space formed of styrene and mercaptocarboxylic acid esters,
The cos θ for the odor of mercaptocarboxylic acid esters is 0.991 to 0.999, and the strength thereof is 1.8 to
2. The electrophotographic apparatus according to item 1, wherein the electrophotographic apparatus is 2.6.

The inventors of the present invention have made earnest studies in view of the above problems, and as a result, as a method of improving the odor at the time of heat fixing due to the toner, a step of forming particles in the aqueous medium of the toner, a perfume treatment. It was manufactured through a process and a drying process and was found to be improved by fixing a toner mass of 4 to 158 g / min, and completed the present invention.

Further, as toner, cos θ for styrene odor in the odor space formed by styrene and n-butyl acrylate is 0.990 to 0.998, and cos θ for n-butyl acrylate is 0.986 to 0.
994 and its strength is 1.8 to 2.6, or c against styrene odor in the odor space formed by styrene and mercaptocarboxylic acid esters
osθ is 0.990 to 0.998, and cosθ to mercaptocarboxylic acid esters is 0.991 to 0.99.
9 and its strength is 1.8 to 2.6, it was clarified that the effect is further exerted.

In general, the emulsion-polymerized toner has excellent image quality, but has a problem of generating a peculiar odor at the time of fixing. Particularly, in the fixing device using the endless belt fixing method, the heat fixing time is long as described above. , The effect of odor becomes obvious. As a means for improving this, the deodorizing means defined in the present invention is provided to solve the problem. Although specific means for the deodorizing step will be described later, it is, for example, addition of a chemical deodorant with an enzyme, a plant extract component, or the like, and addition of a fragrance / masking agent. As the characteristics of the toner, the scent of the toner can be freely set by setting the conditions defined in the present invention, and particularly preferably,
The conditions are defined in claims 2 and 3.

The details of the present invention will be described below. First, the toner according to the present invention will be described.

The present invention is characterized in that it is produced through a step of forming particles in an aqueous medium, a perfume treatment step and a drying step. Further, in the invention according to claim 2, styrene and n are used. The cos θ for the styrene odor in the odor space formed by -butyl acrylate is 0.
990 to 0.998, cos θ for n-butyl acrylate odor is 0.986 to 0.994, and its strength is 1.8 to 2.6, and the invention according to claim 3 Then, cos θ for the styrene odor in the odor space formed by styrene and mercaptocarboxylic acid esters is 0.990 to 0.998, and cos θ for the mercaptocarboxylic acid ester odor is 0.99.
1 to 0.999, and its strength is 1.8 to 2.6.

The perfume treatment step in the present invention is any step until the toner particles containing the resin and the colorant, the particles of which are formed in the aqueous medium, are separated from the aqueous medium,
It means to give a fragrance treatment with a fragrance.

Examples of perfumes that can be used in the present invention are shown below, but the present invention is not limited thereto. Further, in the present invention, a fragrance having not only a scent but also a deodorant function of chemically decomposing an unpleasant odor is preferably used.

(Plant extract component) The plant extract component that can be used in the present invention means an extract derived from a plant, an extract component, or a compound having a structure similar to that of the plant extract component dispersed in water or the like. Refers to something. In the present invention, the deodorant substance related to the plant extract component is preferably a substance that deodorizes a sulfur-based malodorous component, for example, a green tea extract, a plant extract such as persimmon condensed tannin and bamboo extract is preferable,
These have the effect of chemically decomposing hydrogen sulfide, methyl mercaptan, or the like into odorless molecules, or encapsulating (inclusion) these malodorous molecules to deodorize them.

When the flavor containing the plant extract component of the present invention is produced from green tea, crushed raw leaves of tea leaves are soaked in ethanol, and then the catechins, vitamins, sugars and enzymes thus obtained are included. By filtering and concentrating the ethanol extraction solution, the fragrance containing the plant extract component according to the present invention can be obtained. More specifically, it is produced by extracting raw leaves of tea leaves with ethanol at 80 ° C. or lower, for example, ethanol at 50 to 70 ° C., and this solution contains ethanol-soluble components contained in the raw leaves of tea leaves and Including water-soluble ingredients. In the extraction of fresh tea leaves with ethanol, the ethanol extract contains (−)-epicatechin (EC) and (−)-epigallocatechin (Eg).
C), flavanols such as (−)-epicatechin gallate (ECg) and (−)-epigallocatechin gallate (EGCg), enzymes such as oxidoreductase, transferase, hydrolase and isomerase, flavonol Kind, for example,
Flavone, isoflavone, flavonol, flavanone,
Flava reel, auron, antoanidin, chalcone,
It contains substantially the same extract components as green tea extract including dihydrochalcone and the like and glycosides of flavonols, caffeine, amino acids, flavandiols, polysaccharides and proteins, vitamins and the like. Since the raw leaf component of tea leaves varies depending on the weather, temperature, harvest time and place of harvest, it provides a uniform and stable deodorizing duration as a fragrance, and at the same time enhances the deodorizing effect and deodorizing effect of the fragrance. The purified vitamin C and vitamin B1 are preferably added to the ethanol extract at 1 to 2% by mass of the solid content.

The fragrance according to the present invention is an alcohol solution such as ethanol containing catechins, vitamins, sugars and enzymes, and can further contain the extraction residue of alcohol of the raw leaves of tea leaves. Therefore, the fragrance according to the present invention is obtained by immersing a pulverized product of raw tea leaves in alcohol,
It can be produced by extracting the components of tea leaves contained in fresh leaves.

Other specific examples of the fragrance containing the plant extract component include cypress, Aomori hiba, beech, cedar, camphor tree,
Eucalyptus and other trees, herbs, mustard, wasabi, lemon,
Karin, peppermint, clove, Ceylon nikkei, bamboo, Iriomotami rhizome, or Yaeyama palm root, etc., and these extracts are treated by crushing, squeezing, boiling, or steam distillation to extract or extract components. Obtainable. Specific examples of plant-derived extract components or compounds having a structure equivalent to plant extract components include tropolones such as hinokitiol, α-pinene, β-pinene, camphor, menthol, limonene, borneol, α- Monoterpenes such as terpinene, γ-terpinene, α-terpineol, terpinen-4-ol and cineol, sesquiterpenes such as α-casino and t-mullol, polyphenols such as catechin and tannin, 2,3,5- Examples thereof include naphthalene derivatives such as trimethylnaphthalene, long-chain aliphatic alcohols such as citronellol, aldehydes such as cinnamaldehyde, citral and perillaaldehyde, and allyl compounds such as allyl isothiocyanate. When the plant-derived extract component or the synthetic product having the same structure as the plant extract component is insoluble in water, it can be dispersed in water by using a dispersant such as a surfactant.

As the commercially available plant extract component fragrance, for example, F118 (manufactured by Fine 2 Co., Ltd.), Dersen (manufactured by Yutsune Pharmaceutical Co., Ltd.) and the like are preferably used.

In the present invention, at least one of the plant extract components is preferably a phytoncide.

The phytoncide type deodorant is mainly composed of a plant extract containing phytoncide, and has a molecular weight of 15,000 to 2,300,00 extracted from coniferous trees.
Anionic activator, glycols,
It is manufactured by adding a special activator, a host compound, etc., and its effect is to completely chemically decompose the odorous component by the neutralization inclusion method and change it to another substance. As a commercially available product, Biodash D-200 (manufactured by Daiso) is preferably used.

(Vegetable Oil Perfume 1) The material effective in the present invention is a plant essential oil obtained from plants of the Lauraceae family, Apiaceae family, Myrtaceae family, Lamiaceae family, Pinaceae family, Cupressaceae family, and Gramineae family.

Specifically, the following plant essential oils can be mentioned. These indicate that, for example, cinnamon oil is an essential oil extracted from cinnamon by a steam distillation method. Also,
The names of the main constituent compounds in this essential oil component are shown in parentheses. These vegetable essential oils may be used alone or in a mixture.
It is also obvious that the main constituent compound itself may be used.

Examples of camphoraceae include cinnamon oil (cinnamic aldehyde, cinnamaldehyde), camphor oil (linalol), Ravensala oil (1,8-cineole, α-terpineol), Ravensara eugenol oil (1,8-cineole). , Eugenol), rosewood oil (linalol, α-terpineol), bay leaf oil (linalol, 1,8-cineole, eugenol), and the like as cariaceae, for example, caraway oil (d-carvone, limonene), anise. Oils (anethole, anisaldehyde), angelica oil (α-pinene, α-ferrandrene), galvanum oil (pinene, γ-casinoal), carrot seed oil (carrotol), cumin oil (cuminal), coriander oil (linalol, decanal) , Desenal, octaner ), Dill oil (epoxymenthane, ferrandrene, carpon), fennel oil (anethole, fencon), lobedi oil (ptylidenephthalide, β-ferrandrene, terpinyl acetate, ocimene), etc. Clove oil (eugenol acetate, eugenol), caypte oil (1,8-cineole, α-terpineol), tea tree oil (terpinenol-4, γ-terpinene), niauli oil (1,8-cineole, viridiflorol),
Nyauri nerolidol oil (nerolidol), myrtle (myrte or gimpica) oil (1,8-cineole, alpha
-Pinene, geranyl acetate), eucalyptus globulus oil (globulol, pinocarpon, 1,8-cineole), eucalyptus tygeriana (eucalyptus lemon) oil (citral, geranyl acetate), eucarismine oil (α
-Terpineol, 1,8-cineole), eucalyptus dives oil (piperidone, ferradren), eucalyptus radiata oil (α-terpineol, 1,8-cineole), eucalyptus triodora oil (citronellal, citronellol) Examples include sage oil (Tsuyon, camphor), patchouli oil (patchouli alcohol, guaien), lavender (high R lavender) oil (linalyl acetate, linalool), rosemary camphor oil (camphor, 1,8-cineole). , Rosemary cineole oil (1,8-cineole), spearmint oil (L-carpon, limonene), thyme geraniol oil (geraniol, geranyl acetate), thyme thymol oil (thymol, p-cymene), thyme tunanol. Oil (Tunanol-4, Te Pinenoru -4), time
Linalool oil (sinalol, linalyl acetate), Thyme saturioides oil (borneol, α-terpineol, carvacrol), pasil oil (methylcavicol)
As the Pinaceae, for example, cedar wood oil (cadinene, atlanton), pine oil (α-pinene, β-pinene, β-caryophyllene, α-terpineol), pine nut oil (α-pinene, β-pinene). , Siberian peach oil (bornyl acetate, camphene), balsam fir oil (β-pinene, bornyl acetate), as a cypress family,
For example, cypress oil (α-pinene, β-pinene, terpinyl acetate, cedrol), Junivar branch oil (α-pinene, β-pinene, tsuyopsene, sabinene),
Juniper berry oil (α-pinene, terpinenol-
(4, Germacron), and as a Gramineae, for example,
Examples thereof include citronella oil (methylisoeugenol, geraniol), palmarosa oil (geraniol, geranyl acetate), vetiver oil (vetibo), lemongrass oil (geranial, neral, geraniol).

(Vegetable oil flavor 2) The materials effective in the present invention include eugenol, cinnamaldehyde, p-cymene,
Benzaldehyde, benzyl acetate and benzyl benzoate, and is characterized by containing at least one selected from them.

Eugenol includes, for example, Ravensala eugenol (Lauraceae), pasil eugenol (Lamiaceae) and clove (Lupaceae), cinnamaldehyde (cinnamonaceae), and p-cymene thymethymol (Lamiaceae). ), And benzyl benzoate has ylang-ylang (Anemoneaceae).

The plant oil is a flower of various plants,
Aromatic and volatile oils obtained from leaves, fruits, branches, roots, etc.

(Amyris oil-based fragrance) The term “amiris oil” as used in the present invention means Amiris Balsamifella of the Rutaceae family in northern South America.
(fera) is a plant essential oil extracted by steam distillation from xylem and seeds. Its main ingredients are casino, kazinen, and caryophyllene.

The method of use in the present invention is to emulsify amylis oil in water using a surfactant. After this emulsion is subjected to a polymerization reaction or a salting-out / fusion reaction, filtration /
Used as a cleaning solution during cleaning. As a result, it also has a function of reacting with the chain transfer agent remaining on the surface of the colored particles and decomposing and deodorizing the odorous components by a chemical reaction.

(Macrocyclic lactone, macrocyclic ketone compound)
As the macrocyclic lactone compound used as a fragrance,
For example, 14-tetradecanolide, 15-pentadecanolide, 11 (or 12) -pentadecene-15-olide, 16-hexadecanolide and 9-hexadecene-1.
6-olide and the like can be mentioned.

The macrocyclic ketone compound used as a fragrance is, for example, cyclopentadecanone or 3-
Methyl-cyclopentadecanone, cyclohexadecanone, 5-cyclohexadecen-1-one, 8-cyclohexadecen-1-one, cycloheptadecane, 3-ethyl-cyclopentadecanone, 3-propyl-cyclopentadeca Non-, 9-cycloheptadecen-1-one, cycloheneicosanone, 3-methyl-cycloheneicosanone, 11-cycloheneicosen-1-one and the like can be mentioned.

(Pyruvate) In the present invention, it has been found that a highly safe and effective perfume effect can be obtained by using the following pyruvate.

[0043]

[Chemical 1]

Here, R represents a linear, branched or cyclic alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms. More specifically, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, 2- Examples thereof include groups such as ethylhexyl group, decyl group, cyclopentyl group, cyclohexyl group, and examples of aryl groups include phenyl group, and substituted phenyl groups such as tolyl group and p-chlorophenyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, p-isopropylbenzyl group and the like. Examples of the aralkyl group include a norbornyl group, a citronellyl group and a geranyl group.

Regarding the use of these compounds, they can be used alone or as a mixture. Pyruvate can be prepared by esterifying pyruvate by a known method, or by oxidizing lactic acid ester.

The method of use is to first emulsify the pyruvic acid esters in water using a surfactant. Next, at the time of washing, the amount of pyruvic acid ester is 0.0
It is preferable to add the toner particles to the cleaning liquid of the toner particles so that the content of the toner particles is about 1 to 1% by mass. Repeating this step may increase the effect, and thus may be repeatedly washed.

(Auxiliary Deodorant) In the present invention, the polymerizable monomer is polymerized in an aqueous medium, and water is removed before the toner particles containing at least the resin and the colorant are separated from the aqueous medium. It is preferable to treat with a deodorant solution dissolved or dispersed in the above. Specifically, in the polymerization step which is a toner manufacturing step, the salting out / fusion step, the solid-liquid separation step, the drying step, and the external addition step, the polymerization is performed. It is particularly preferable to perform the deodorizing treatment in any of the steps from the solid-liquid separation step.

The deodorant solution according to the present invention contains 50% by mass or more of water, and may further contain alcohols, alcohol amines, surfactants, and organic acids such as citric acid.

(Adsorption of perfume on the surface of toner particles) In the present invention, the perfume is adhered to the surface from the viewpoint of maintaining the deodorizing effect even if the odor component of the toner exudes from the inside of the toner after drying or after hermetically packaging. It is preferable to take an adsorbed state. The method of adsorption is not particularly limited, but it is preferable to dissolve or disperse the fragrance in an aqueous medium in which the toner is polymerized and salted out and aggregated. In the toner filtration washing step described later, a surfactant or a salting out agent is added. After removing the kimono, it is particularly preferable to treat with a high-concentration fragrance liquid. The perfume concentration to be adsorbed is 0.01 to 10 with respect to the toner.
It is preferably ppm. If it is 0.01 ppm or less, the deodorizing action is not long-lasting, and if it is 10 ppm or more, the charging characteristics are not stable.

Further, in a polymerization toner comprising a resin and a colorant formed by polymerizing a radical polymerizable monomer containing each chain transfer agent described later in an aqueous medium, the radical polymerization in the polymerization toner is performed. It is preferable that the amount of the polymerizable monomer is 200 ppm or less and the amount of the chain transfer agent is 50 ppm or less. For that purpose, at least a water-soluble polymerization initiator is used in an aqueous medium, and resin particles formed by polymerizing a radical-polymerizable monomer containing a chain transfer agent are melted in an aqueous medium. In the method for producing the legal toner, it is preferable to add the water-soluble polymerization initiator a plurality of times to produce the toner.

Next, regarding the odor space according to the present invention,
This will be described below. The odor space referred to in the present invention is a space obtained by measurement using an odor discrimination device FF-1 (manufactured by Shimadzu Corp.), for example, 1) styrene, 2) n-butyl alcohol, 3) mercaptocarboxylic acids. (Preferably, using a sample prepared by mixing any compound containing n-octylmercaptopropionic acid) 1), 2)
And 3) is a space in which the vector on the principal component analysis that changes when the amount is increased is represented as coordinates, and is an index indicating the quality of odor generated.

In the present invention, the angle of each vector between the odor-causing substance in the toner and the sample is obtained, and its cosine (cos) is obtained.
θ) is calculated. At this time, the smaller the vector angle,
That is, it can be said that the larger the value of cos θ, the more the sample has an odor similar to the odor-causing substance.

For example, it is assumed that the vectors of the toners a and b are shown together with the vector of the standard substance, as shown in FIG. In this case, since cos θb> cos θa, the toner b is closer to the odor of the standard substance.

The method of measuring cos θ for a specific substance in the odor space in the present invention is as follows.

As a measurement sample, 0.1 g of toner is put in a 2 liter sample bag made of polyethylene terephthalate.

After filling with nitrogen gas, 1 together with the sample bag
Heat for 30 seconds on a hot plate at 60 ° C.

Preparation of Standard Sample Standard sample for styrene odor: 0.2 ml of styrene saturated gas was placed in a 2 liter sample bag and diluted with nitrogen gas.

Here, the saturated gas means a gas collected by a microsyringe from the vicinity of the liquid surface of a reagent bottle which is hermetically stored at room temperature.

Standard sample for n-butyl acrylate odor: 2
0.2 ml of n-butyl acrylate saturated gas is placed in a liter sample bag and diluted with nitrogen gas.

Standard sample for odor of mercaptocarboxylic acid esters: As a standard sample, n-octyl-3-mercaptopropionic acid ester is used. A 2-liter sample bag was charged with 0.5 ml of n-octyl-3-mercaptopropionate saturated gas, diluted with nitrogen gas, and left for 1 hour.

Measuring conditions Measuring device: Odor identification device FF-1 (manufactured by Shimadzu Corporation) Sensor room temperature 60 ° C. Sampling flow rate: 165 ml / min Pre-sampling time: 10 seconds Sampling time: 45 seconds Collection tube temperature: 40 ° C. Dry Purge temperature: 40 ° C, flow rate: 500 ml / min, time: 45 seconds Desorption collection tube temperature: 220 ° C, time: 90 seconds, flow rate: 20 ml
/ Minute number of times per sample: 5 times In the present invention, there is no particular limitation on the method for providing the odor space defined in claim 2 or 3, but it is achieved by appropriately selecting or combining the above-mentioned various flavors. be able to.

Further, in the polymerized toner according to the present invention, it is preferable to use a chain transfer agent having a small odor as the chain transfer agent itself. The chain transfer agents which can be used in the present invention are listed below. Is not limited to these.

Examples of the chain transfer agent that can be used in the present invention include the following general formula (1) or general formula (2).
The compound represented by can be mentioned.

General formula (1) HS-R ₁ -COOR ₂ (In the formula, R ₁ has ₁ to 10 carbon atoms which may have a substituent.
R ₂ is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. ) The general formula (1)
As preferred compounds, thioglycolic acid esters and 3-mercaptopropionic acid esters can be mentioned. Specifically, as thioglycolate esters, ethyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, Examples include dodecyl thioglycolate, thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, thioglycolic acid ester of trimethylolpropane, thioglycolic acid ester of pentaerythritol, and thioglycolic acid ester of sorbitol. , 3-mercaptopropionic acid esters include ethyl esters,
Octyl ester, decyl ester, dodecyl ester, pentaerythritol tetrakis ester, ethylene glycol 3-mercaptopropionic acid ester,
Examples thereof include 3-mercaptopropionic acid ester of neopentyl glycol, 3-mercaptopropionic acid ester of trimethylolpropane, 3-mercaptopropionic acid ester of pentaerythritol, and 3-mercaptopropionic acid ester of sorbitol.

General formula (2) HS-R ₃ (In the formula, R ₃ has 1 to 20 carbon atoms which may have a substituent.
Represents a hydrocarbon group of. ) Preferred examples include n-octyl mercaptan, 2-ethylhexyl mercaptan, n-dodecyl mercaptan, sec-dodecyl mercaptan and t-dodecyl mercaptan.

As another preferable chain transfer agent, a terpene compound can be mentioned. There are some terpene-based compounds that have the same performance as a mercaptan-based compound as a chain transfer agent and that do not generate an odor during fixing by heating. That is, in the toner according to the present invention, it is preferable that among the terpene-based compounds, resin fine particles prepared by a polymerization method using a mono- or sesquiterpene-based compound as a chain transfer agent are used. Further, among the monoterpene compounds, particularly preferable compounds are α-pinene, β-pinene, 3-carene, camphene, limonene, terpinolene, α-terpinene, myrcene, α-terpineol, β-terpineol, linalool, nerol. , Geraniol, and particularly preferred compounds among the sesquiterpene compounds include apple forene and caryophyllene.

The monoterpene compound and sesquiterpene compound chain transfer agent which can be used in the present invention are conventionally known thioglycerin, thioglycolic acid, thioglycolic acid ester, mercaptan compound, carbon tetrachloride, chloroform. Can be used in the same manner as chain transfer agents such as.

In the present invention, the amount of the monoterpene compound or sesquiterpene compound used is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, based on the radical-polymerizable monomer composition. It is 4% by mass. 0.
If the amount is less than 01% by mass, the effect cannot be exhibited.
If the amount exceeds the mass%, the chain transfer agent remains unreacted, which is not preferable.

Other preferable chain transfer agents include:
A mercaptosilane chain transfer agent can be used.

Examples of the mercaptosilane chain transfer agent which can be used in the present invention include mercaptomethyldimethoxysilane, mercaptomethyldiethoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane and 2-mercaptoethyldimethoxy. Silane, 2-mercaptoethyldiethoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyldiethoxysilane, 3
-Mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 4-mercaptobutylethyldimethoxysilane, 4-mercaptobutylethyldiethoxysilane, 8-mercaptooctylethyldimethoxysilane, 8-mercaptooctylethyldiethoxysilane,
12-mercaptododecylethyldimethoxysilane, 1
2-mercaptododecylethyldiethoxysilane etc. can be mentioned. The amount of the above compound used is preferably 0.01 to 5% by mass based on the total mass of the toner.

As other preferable chain transfer agents, known water-soluble chain transfer agents can be used, and examples thereof include sodium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium pyrosulfite, chloromethanol, 2-chloroethanol, 1-chloro-2
-Propanol, 2-chloro-n-propanol, 3-
Chloro-n-propanol, 2-chloro-n-butanol, 3-chloro-n-butanol, 4-chloro-n-butanol, chloropentanol, chlorohexanol,
Chloroheptanol, chlorooctanol, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, chlorodifluoroacetic acid, α-chloropropionic acid, β-chloropropionic acid, p-chlorobenzoic acid, 2-chloro-6-fluorobenzoic acid, α- Bromopropionic acid, β-bromopropionic acid, 2-bromo-n-valeric acid, 5-bromovaleric acid,
11-undecanoic acid, α-bromophenylacetic acid, p-bromophenylacetic acid, 2-bromooctanoic acid, 2-bromopentanoic acid, 2-bromohexanoic acid, 6-bromohexanoic acid, chlorosuccinic acid, chlorofumaric acid, chloromaleic acid Acid, chloromalonic acid, etc. are mentioned.

Next, a method for producing the toner used in the present invention will be described. (Toner Production Method) In the toner production method according to the present invention, the polymerizable monomer is polymerized in an aqueous medium.
There are two characteristics. That is, when forming the resin particles (nucleus particles) or the coating layer (intermediate layer) containing the release agent, the release agent is dissolved in the monomer, and the resulting monomer solution is used as an oil in an aqueous medium. In this method, latex particles are obtained by dispersing in drops, adding a polymerization initiator to this system, and subjecting to a polymerization treatment.

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

An example of the method for producing the toner according to the present invention is shown below. The toner manufacturing process mainly includes the following processes.

1: Multi-step polymerization step (I) for obtaining composite resin particles in which a release agent and / or crystalline polyester is contained in a region other than the outermost layer (central portion or intermediate layer) 2: Composite resin particles Salting out / fusing step (II) of salting out and fusing the colorant particles with the colorant particles to filter out the toner particles from the dispersion system of the toner particles, and from the toner particles to the surfactant. Filtering / washing step for removing the like and the like 4: Drying step for drying the washed toner particles, 5: Adding an external additive to the dried toner particles.

Each step will be described in detail below. [Multistage Polymerization Step (I)] The multistage 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 multistage polymerization method. Is.

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

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

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

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

Then, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the dispersion liquid of the resin particles,
Polymerization of monomer L in the presence of resin particles (second stage polymerization)
Is a method of forming a coating layer made of a low molecular weight resin (polymer of monomer L) on the surface of the resin particles.

<Three-step polymerization method> The three-step polymerization method comprises a central portion (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. It is a method for producing composite resin particles. That is, the composite resin particles obtained by the three-step polymerization method are composed of a core and two coating layers.

This method will be described in detail. First, a dispersion liquid 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). In addition to the addition, a monomer solution obtained by dissolving the release agent in the monomer M is dispersed in the aqueous medium as an oil droplet, and then the system is subjected to a polymerization treatment (second-stage polymerization).
On the surface of the resin particles (core particles), a coating layer (intermediate layer) made of a resin (polymer of the monomer M) containing a release agent is formed to form composite resin particles (high molecular weight resin-intermediate molecular weight resin). )
A dispersion liquid is prepared.

Then, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the obtained dispersion liquid of the composite resin particles, and the monomer L is polymerized 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 surface 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.

A polymerization method suitable for forming resin particles or a coating layer containing a release agent is as follows. An aqueous medium prepared by dissolving a surfactant at a concentration not higher than the critical micelle concentration is used.
A monomer solution in which a release agent is dissolved in a monomer is used to prepare a dispersion liquid by dispersing oil droplets using mechanical energy, and a water-soluble polymerization initiator is added to the obtained dispersion liquid, A method of radical polymerization in oil droplets (hereinafter referred to as "miniemulsion method" in the present invention) can be mentioned, and the effects of the present invention can be more exerted, which is preferable. In the above method, an oil-soluble polymerization initiator may be used instead of the water-soluble polymerization initiator or together with the water-soluble polymerization initiator.

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

Here, the disperser for dispersing the oil droplets by mechanical energy is not particularly limited, and for example, a stirrer "CLEARMIX" (M -Technique Co., Ltd.), an ultrasonic disperser, a mechanical homogenizer, a Manton Gaulin, a pressure homogenizer, and the like. The dispersed particle size is 1
0 to 1000 nm, preferably 50 to 1000 n
m, and more preferably 30 to 300 nm.

As another polymerization method for forming the resin particles containing the release agent or the coating layer, an emulsion polymerization method,
Known methods such as a suspension polymerization method and a seed polymerization method can also be adopted. In addition, these polymerization methods include resin particles (core particles) or a coating layer that form composite resin particles,
It can also be employed to obtain a release agent and a crystalline polyester-free material.

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

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. [Salting out / fusion step (II)] This salting out / fusion step (II)
Is an indefinite shape (non-spherical shape) by salting out / fusing the composite resin particles obtained by the multi-step polymerization step (I) and the colorant particles (progressing salting out and fusing at the same time).
This is a step of obtaining the toner particles of.

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 salt. In addition, fusion means to eliminate the interparticle interface between resin particles aggregated by the salting out. The salting-out / fusion of the present invention refers to the two steps of salting-out and fusion occurring in sequence, or the action of causing them to occur in sequence. In order to perform salting out and fusion at the same time, particles (composite resin particles, colorant particles) are formed under the temperature condition of the glass transition temperature (Tg) of the resin constituting the composite resin particles or higher.
Need to be aggregated.

In this salting-out / fusion step (II), internal additive particles such as charge control agents (fine particles having a number average primary particle diameter of about 10 to 1000 nm) are salted out together with the composite resin particles and the colorant particles. / May be fused. Further, the colorant particles may be surface-modified, and as the surface-modifying agent,
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 the 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 stirring device "CLEARMIX (CLEAR) equipped with a rotor rotating at high speed.
MIX) ”(manufactured by M Technique Co., Ltd.), ultrasonic disperser, mechanical homogenizer, manton-goulin, pressure homogenizer such as pressure homogenizer, and medium type disperser such as Getzman mill and diamond fine mill.

In order to salt out / fuse the composite resin particles and the colorant particles, the salting out agent (aggregating agent) having a critical coagulation concentration or more is added to the dispersion liquid in which the composite resin particles and the colorant particles are dispersed. ) Is added and the dispersion is heated to the glass transition temperature (Tg) or higher 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.). In addition, an organic solvent infinitely soluble in water may be added in order to effectively carry out the fusion.

[Filtration / Washing Step] In this filtration / washing step, a filtering treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above step and the filtered toner particles (cake-shaped A cleaning process is performed to remove deposits such as surfactants and salting-out agents from the aggregate.

Here, the filtration method is not particularly limited, such as a centrifugation method, a vacuum filtration method using a Nutsche or the like, or a filtration method using a filter press or the like.

[Drying Step] In this step, the washed toner particles are dried.

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

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

It should be noted that the toner particles that have been dried are
When the aggregates are aggregated by the weak attraction between particles, the aggregates may be crushed. Here, as the disintegration processing device,
A mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill or a food processor can be used.

The toner according to the present invention forms composite resin particles in the absence of a colorant, and adds the dispersion liquid of the colorant particles to the dispersion liquid of the composite resin particles to obtain the composite resin particles and the colorant particles. Is preferably prepared by salting out / fusing.

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

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

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

Next, each constituent factor used in the toner manufacturing process will be described in detail. (Polymerizable Monomer) As the polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is used as an essential constituent component, and a crosslinkable monomer is added as necessary. Used. Further, as described below, at least 1 monomer having an acidic polar group or a monomer having a basic polar group is used.
It is desirable to include a kind.

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

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

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

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

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

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

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

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

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

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

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

(4) Monomer Having Basic Polar Group As the monomer having a basic polar group, (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 acid ester of an aliphatic alcohol, (ii) (meth)
Acrylic amide or optionally 1 to 18 carbon atoms on N
(Meth) acrylic acid amide mono- or di-substituted by an alkyl group, (iii) a vinyl compound substituted by a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-
Examples thereof include alkylamines and quaternary ammonium salts 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 the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the above. Quaternary ammonium salt of 4 compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
3-methacryloxypropyl trimethyl ammonium salt etc. can be mentioned.

The (meth) acrylic acid amide of (ii) or the (meth) acrylic acid amide optionally substituted with mono- or dialkyl on N includes acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, Methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide,
N-octadecyl acrylamide etc. can be mentioned.

The vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) is vinyl pyridine,
Examples thereof include vinylpyrrolidone, vinyl-N-methylpyridinium chloride and vinyl-N-ethylpyridinium chloride.

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

(Polymerization Initiator) The radical polymerization initiator used in the present invention can be appropriately used if it is water-soluble. For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.), azo compounds (eg, 4,4 ′)
-Azobis-4-cyanovaleric acid and its salts, 2,2'-azobis (2-amidinopropane) salt, etc.), peroxide compounds and the like. Furthermore, 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 type initiator is preferable because the polymerization activity can be increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.

Any temperature may be selected as the polymerization temperature as long as it is at least the minimum radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C. to 90 ° C. is used. However, it is also possible to polymerize at room temperature or higher by using a combination of a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid, etc.).

(Surfactant) In order to carry out miniemulsion polymerization using the above-mentioned polymerizable monomer, it is preferable to use a surfactant to disperse oil droplets in an aqueous medium. The surfactant that can be used in this case is 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,
Aryl alkyl polyether sodium sulfonate,
3,3-disulfone diphenylurea-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, etc.), sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Examples thereof include fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.).

Further, nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, Examples thereof include sorbitan ester.

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

(Molecular Weight Distribution of Resin Particles and Toner) The toner according to the present invention has a peak or shoulder of 100,000 to
1,000,000, and 1,000-50,000
Preferably, the peak or shoulder is 1
0,000-1,000,000, 25,000-1
More preferably it is present at 50,000 and 1,000 to 50,000.

The molecular weight of the resin particles is 100,000 to
A resin containing at least both 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 preferable. More preferably, it is preferable to use an intermediate molecular weight resin having a peak or a shoulder at the peak molecular weight of 15,000 to 100,000.

The method for measuring the molecular weight of toner or resin is as follows:
Measurement by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent is good. That is, 1.0 ml of THF is added to 0.5 to 5 mg of the measurement sample, more specifically 1 mg, and stirred at room temperature using a magnetic stirrer or the like to sufficiently dissolve the sample. Then, pore size 0.45-0.50
After processing with a μm membrane filter, it is injected into GPC. The measurement conditions of GPC are as follows: stabilize the column at 40 ° C., flow THF at a flow rate of 1.0 ml per minute, and
About 100 μl of a sample having 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 combinations, Tosoh TSKgel G1000H, G2000H,
G3000H, G4000H, G5000H, G600
0H, G7000H, TSKguard column
And the like. A refractive index detector (IR detector) or a UV detector may be used as the detector. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve prepared using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing the calibration curve.

(Aggregating agent) The aggregating agent used in the present invention is
Those selected from among the metal salts are preferred.

Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium, divalent metal salts such as alkaline earth metal salts such as calcium and magnesium, and manganese and copper. Valuable metal salt, iron,
Examples 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,
Examples of 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. Generally, 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 as used in the present invention is an index relating to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at the point where coagulation occurs when a coagulant is added. This critical coagulation concentration greatly changes depending on the latex itself and the dispersant. For example, Seizo Okamura et al., Polymer Chemistry 17,601
(1960) and the like, and the value can be known by following these descriptions. Also, as another method,
It is also possible to add a desired salt to the target particle dispersion liquid while changing the concentration, measure the ζ potential of the dispersion liquid, and set the salt concentration at the point where the ζ potential starts to change to the critical aggregation concentration.

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

The concentration of the metal salt as the aggregating agent in the present invention may be the critical coagulation concentration or more, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical coagulation concentration.

(Colorant) The toner according to the present invention is obtained by salting out / fusing the above-mentioned composite resin particles and colorant particles.

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

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

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

When used as a magnetic toner, the above magnetite can be added. In this case, from the viewpoint of imparting a predetermined magnetic characteristic, 20 to 6 is contained in the toner.
It is preferable to add 0% by mass.

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

As the magenta or red pigment,
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
Etc.

Examples of pigments for orange or yellow include C.I. I. Pigment Orange 31, C.I.
I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. 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.

As the pigment for green or cyan,
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.

Examples of dyes include C.I. I. Solvent Red 1, 49, 52, 58, 63,
111, 122, C.I. I. Solvent yellow 1
9, the same 44, the same 77, the same 79, the same 81, the same 82, the same 9
3, ibid 98, ibid 103, ibid 104, ibid 112, ibid 16
2, C.I. I. Solvent Blue 25, 36, 60,
No. 70, No. 93, No. 95 and the like can be used, and a mixture thereof can also be used.

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

The colorant (colorant particles) constituting the toner according to 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 or the like can be preferably used. As the silane coupling agent, for example, methyltrimethoxysilane, phenyltrimethoxysilane,
Alkoxysilanes such as methylphenyldimethoxysilane and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxy. Examples thereof include silane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane. As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 1 marketed under the trade name "Planeact" manufactured by Ajinomoto Co., Inc.
38S, 238S, etc., commercial products A-1, 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 can be mentioned. As the aluminum coupling agent, for example,
Examples include "Planeact AL-M" manufactured by Ajinomoto Co., Inc.

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

Examples of the method for modifying the surface of the colorant particles include a method in which a surface modifier is added to a dispersion of the colorant particles and the system is heated to react.

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

(Release Agent) The toner used in the present invention is
It is preferable that the toner is obtained by fusing resin particles containing a release agent in an aqueous medium. Thus, by salting out / fusing the resin particles in which the release agent is included in the resin particles with the colorant particles in the aqueous medium, a toner in which the release agent is finely dispersed can be obtained.

In the toner according to the present invention, the release agent is
Low molecular weight polypropylene (number average molecular weight = 1500-9
000) and low molecular weight polyethylene are preferable, and ester compounds represented by the following formulas are particularly preferable.

In the formula R ^1- (OCO-R ² ) _n , 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.

[0160]

[Chemical 2]

[0161]

[Chemical 3]

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

The toner according to the present invention is preferably prepared by encapsulating the above-mentioned releasing agent in resin particles by a mini-emulsion polymerization method and salting out and fusing with the toner particles.

(Charge control agent) To the toner, in addition to a colorant and a release agent, a material capable of imparting various functions as a toner material can be added. Specific examples include charge control agents. These components can be added by various methods such as a method of adding the resin particles and the colorant particles at the same time as the salting-out / fusing step and incorporating them into the toner, a method of adding them to the resin particles themselves.

As the charge control agent, various known agents can be used, which can be dispersed in water. Specific examples thereof include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

(External Additive) A so-called external additive can be added to the toner according to the present invention for the purpose of improving fluidity and cleaning property. 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 which can be used as the external additive, conventionally known ones can be mentioned. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

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

Specific examples of 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, MT-1 manufactured by Teika Co., Ltd.
00B, MT-500BS, MT-600, MT-60
0SS, JA-1, commercial product TA- manufactured by Fuji Titanium Co., Ltd.
300SI, TA-500, TAF-130, TAF-
510, TAF-510T, commercial products IT-S, IT-OA, IT-OB, IT-OC manufactured by Idemitsu Kosan Co., Ltd. and the like can be mentioned.

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

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

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

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

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

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

(Toner Particles) The toner according to the present invention preferably has a number average particle diameter of 3 to 10 μm, more preferably 3 to 8 μm. This particle size is
In the toner production method, it can be controlled by the concentration of the aggregating agent (salting out agent), the addition amount of the organic solvent, the fusing time, and the composition of the polymer.

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

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

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

<Preferred Shape Factor Range of Toner Particles>
The toner according to the present invention has a shape factor of 1.0 to 1.6 with 65% by number or more, preferably 1.2 to 1.6 with 65% by number or more, particularly preferably 1.2 to 1 No. 0.6 is 70% by number or more.

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

Shape factor = ((maximum diameter / 2) 2 × π) / projected area Here, the maximum diameter is the parallel line when a projected image of toner particles on a plane is sandwiched by two parallel lines. Refers to the width of the particles at which the interval is maximum. The projected area means the area of the projected image of the toner particles on the plane. In the present invention, this shape factor is obtained by taking a photograph of the toner particles magnified 2000 times with a scanning electron microscope, and then based on the photograph, "SCANNING IMAGE ANALYZE
R ”(manufactured by JEOL Ltd.) was used to measure the photographic image. At this time, the shape factor of the present invention was measured by the above calculation formula using 100 toner particles.

In the toner according to the present invention, when the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution of, the sum 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 next most frequent class ( It is preferable that the toner M) is 70% or more.

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

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

[Measurement conditions] 1: Aperture: 100 μm 2: Sample preparation method: Electrolyte solution [ISOTON R-11
(Made by 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 an ultrasonic disperser for 1 minute.

(Developer) The toner according to the present invention may be used as a one-component developer or a two-component developer.

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

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

The volume average particle diameter of the carrier is typically measured by a laser diffraction type particle size distribution measuring apparatus "HELOS" equipped with a wet disperser (SYMPATIC (SYMP).
(Made by ATEC)).

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

(Image Forming Method) An example of the electrophotographic apparatus of the present invention will be described.

FIG. 2 is a schematic block diagram of an electrophotographic apparatus showing an embodiment of the present invention. Reference numeral 4 denotes a photoconductor, which is a typical example of the electrostatic latent image forming member in the present invention. An organic photoconductor (OPC), which is a photosensitive layer, is formed on the outer peripheral surface of an aluminum drum base, and rotates in the direction of the arrow at a predetermined speed. In this embodiment, the photoconductor 4 has an outer diameter of 60 mm.

In FIG. 2, exposure light is emitted from the semiconductor laser light source 1 based on information read by a document reading device (not shown). This is distributed by the polygon mirror 2 in the direction perpendicular to the paper surface of FIG. 2, and is irradiated on the surface of the photoconductor through the fθ lens 3 that corrects image distortion to form an electrostatic latent image. The photoconductor is previously uniformly charged by the charger 5, and starts rotating clockwise in accordance with the timing of image exposure.

The electrostatic latent image on the surface of the photoconductor is developed by the developing device 6, and the formed developed image is transferred by the operation of the transfer device 7 to the recording material 8 which is conveyed at a timing. Further, the photoreceptor 4 and the recording material 8 are separated by a separator (separation pole) 9, but the toner development image is transferred and carried on the recording material 8 and guided to a fixing device 10 to be fixed.

The toner according to the present invention is suitable for use in an image forming method including a step of passing a transfer material on which a toner image is formed between a heating roller and a pressure roller constituting a fixing device to fix the transfer material. To be done.

The fixing device preferably used in the present invention will be described below. FIG. 3 is a schematic sectional view showing an example of a heating roller type fixing device used in an electrophotographic apparatus using the toner according to the present invention. The fixing device shown in FIG. And a pressure roller 70 in contact therewith. In FIG. 3, T is an undeveloped toner image formed on the transfer material (base material) 8, and T ′ is a fixed toner image.

The heating roller 80 has a coating layer 82 made of fluororesin or an elastic material formed on the surface of a cored bar 81, and contains a heating member 75 made of a linear heater.

The core metal 81 is made of metal and has an inner diameter of 10 to 70 mm. The metal forming the core metal 81 is not particularly limited, but examples thereof include metals such as iron, aluminum and copper, and alloys thereof.

The core 81 has a wall thickness of 0.1 to 15 mm, and is determined in consideration of the balance between the demand for energy saving (thinning) and the strength (depending on the constituent materials). For example,
In order for the core metal made of aluminum to maintain the same strength as the core metal made of iron of 0.57 mm, it is necessary to make the wall thickness 0.8 mm.

Examples of the fluororesin constituting the surface layer 71 of the coating layer 82 include PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer).

The coating layer 82 made of fluororesin has a thickness of 1
The thickness is 0 to 500 μm, and preferably 20 to 400 μm.

Surface layer 7 of coating layer 82 made of fluororesin
When the thickness of 1 is less than 10 μm, the function as the surface layer cannot be sufficiently exerted, and the durability as the fixing device cannot be secured. On the other hand, if it exceeds 500 μm, the surface is easily scratched by paper dust, and toner or the like adheres to the scratched portion, resulting in the problem of image smearing.

Further, as the elastic body forming the coating layer 82, it is preferable to use silicone rubber such as LTV, RTV, HTV and the like having good heat resistance and silicone sponge rubber.

Asker C, which is an elastic body forming the coating layer 82
The hardness is less than 80 °, preferably less than 60 °.

The thickness of the coating layer 82 made of an elastic material is 0.1 to 30 mm, preferably 0.1 to 20 mm.
It is said that

Asker C, which is an elastic body forming the coating layer 82
When the hardness exceeds 80 ° and the thickness of the coating layer 82 is less than 0.1 mm, the fixing nip cannot be increased, and the effect of soft fixing (for example, smoothed interface Effect of improving color reproducibility by toner layer)
Can't exert.

A halogen heater can be preferably used as the heating member 75. The pressure roller 70 has a coating layer 84 made of an elastic material formed on the surface of the cored bar 83. The elastic body forming the coating layer 84 is not particularly limited, and various soft rubbers such as urethane rubber and silicone rubber and sponge rubber can be exemplified, and it is preferable to use silicone rubber and silicone sponge rubber.

Asker C, which is an elastic body forming the coating layer 84
The hardness is less than 80 °, preferably less than 70 °, and more preferably less than 60 °.

The coating layer 84 has a thickness of 0.1 to 30 m.
m, preferably 0.1 to 20 mm.

Asker C, which is an elastic body forming the coating layer 84
If the hardness exceeds 80 ° and the thickness of the coating layer 84 is less than 0.1 mm, the fixing nip cannot be increased and the soft fixing effect cannot be exhibited.

The material constituting the cored bar 83 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 80 and the pressure roller 70 is usually 40 to 350 N,
Preferably 50-300 N, more preferably 50-2
It is set to 50N. The contact load is defined in consideration of the strength of the heating roller 80 (the thickness of the cored bar 81), and is, for example, 0.
For a heating roller having a cored bar made of iron of 3 mm, it is preferably 250 N or less.

From the viewpoint of offset resistance and fixing property, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ^{5 to} 1.5 × 1.
It is preferably 0 ⁵ Pa.

If one example of the fixing conditions by the fixing device shown in FIG. 3 is shown, the fixing temperature (surface temperature of the heating roller 80) is 1
50 to 210 ° C., fixing linear velocity is 80 to 640 mm /
It is assumed to be sec.

FIG. 4 is a schematic sectional view showing another example of a heating roller type fixing device used in the electrophotographic apparatus using the toner according to the present invention.

As shown in FIG. 4, a heating roller 80, a pressure roller 70, and heating members 75 and 75 'serving as heating means.
The base material 8 carrying the unfixed toner image T is conveyed between the heating roller 80 and the pressure roller 70 to perform the fixing process.

The heating roller 80 includes a core metal 81 made of aluminum or the like, and a coating layer 82 and a surface layer 71 on the core metal 81.
May be provided in this order, and a primer layer may be provided between the layers as necessary. The constituent layers of the heating roller 80 are the same as those shown in FIG.
It is preferable to use the same material and structure as those described for the heating roller 80 of FIG.

On the other hand, the pressure roller 70 has a cored bar 83 made of aluminum or the like, a coating layer 84 and a surface layer 85 on the cored bar 83 in this order, and a primer layer is provided between the layers as necessary. Is also good. Each constituent layer of the pressure roller 70 is preferably made of the same material and structure as those described for the heating roller 80 in FIG.

The pressure roller 70 is a spring (not shown).
Is pressed against the heating roller 80, and the nip width is formed by an appropriate pressing force.

The heating roller 80 is rotated by a driving force transmitted from a motor (not shown) through a gear (not shown), and the pressure roller 70 is driven to rotate accordingly. About 1 kV to the core metal 81 of the heating roller 80
A DC bias of 2 kV (polarity opposite to the polarity of the unfixed image) is applied by the high voltage power source, and electrostatic offset of the toner and disturbance of the unfixed image near the nip are prevented.

Further, the core 1 of the pressure roller 70 is connected to the diode 1 and the current limiting protection resistance of the diode, and the surface potential of the pressure roller 70 is the polarity of the unfixed image (in the present embodiment, Negative) and reverse polarity (in this embodiment,
It becomes easy to become positive).

The heating members 75 and 75 'are respectively provided with a core metal 8
1, 83 are disposed inside. The temperature of the heating roller 80 and the pressure roller 70 is detected by the temperature sensors 86 and 86 ', and the temperature of the surface is set to a preset value.
The heater driving circuit controls the lighting of the heating members 75 and 75 'to control the temperature.

Further, the heating roller 80 and the pressure roller 70 are rotationally driven so that the peripheral speed becomes about 120 mm / s.

The base material 8 which is a recording medium is guided so as to enter the nip portion by the input guide, and is nipped and conveyed by the heating roller 80 and the pressure roller 70, and the unfixed toner image T on the base material 8 is heated and fixed. To be done.

FIG. 5 is a schematic sectional view showing an example of an endless belt type fixing device used in the electrophotographic apparatus using the toner according to the present invention.

In FIG. 5, a heating roller 80 containing a heating member 75, an endless belt 90 arranged so as to be in pressure contact with the heating roller 80, a pressure roller 70 for stretching the endless belt 90 and two rollers. The support rollers 91 and 92 and the pressure support roller 93 that presses the endless belt 90 against the heating roller 80 to form a nip portion are mainly configured.

The heating roller 80 is formed by forming a coating layer 82 made of an elastic body and a surface layer (also referred to as a release layer) 71 around a metal cored bar 81. The cored bar 81 is made of, for example, iron. , A cylinder made of aluminum, SUS, or the like. A coating layer 82 is provided on the surface of the cored bar 81. As the covering layer 82, an elastic body having high heat resistance can be used, and for example, the rubber hardness is 45 ° (J
HTV (High Temperature) of IS-A
Vulcanization) silicone rubber can be formed with the desired thickness, and other materials can be used. A release layer 5 is provided on the cover layer, and for example, RTV (Room Tempe) is provided.
(Ruture Vulcanization) In addition to silicone rubber, fluoro rubber such as Viton and PFA
(Perfluoroalkoxy vinyl ether copolymer resin), PTFE (polytetrafluoroethylene), FE
P (tetrafluoroethylene hexafluoropropylene copolymer resin)
The release layer can be formed by using a method such as dip coating.

The cored bar 81 may be made of metal such as aluminum or SUS other than iron. As the surface layer 71, in addition to silicone rubber, fluorine rubber such as Viton, PFA (perfluoroalkoxy vinyl ether copolymer resin),
A fluororesin such as PTFE (polytetrafluoroethylene) or FEP (tetrafluoroethylene hexafluoropropylene copolymer resin) may be coated.

A heating member 75 such as a halogen lamp is fixedly supported inside the core metal 81 as a heating source. Further, a temperature sensor 86 is arranged close to the surface of the heating roller 80, and the temperature of the surface of the heating roller 80 is measured. The heating member 75 is feedback-controlled by a temperature controller (not shown) based on the measurement signal of the temperature sensor 86, and the surface of the heating roller 80 is adjusted to a prescribed temperature.

The endless belt 90 comprises the pressure roller 70.
Further, it is stretched around the support rollers 91 and 92 with a constant tension. The pressure roller 70 and the support rollers 91 and 92 are mainly made of stainless steel or the like.
Of these, the pressure roller 70 is pressed toward the center of the heating roller 80 with a desired load, whereby the endless belt 90 is pressed against the heating roller 80 so as to be wound. The nip width (the length of the recording sheet in the conveyance direction) at this time is usually about 20 mm.

A surface layer 94 may be provided on the endless belt 90. For example, 3 parts of low molecular weight tetrafluoroethylene resin particles or polyfluoroalkyl vinyl ether (PFA) resin particles may be used per 100 parts by mass of fluororubber. It is preferable to use a vulcanized product of a fluororubber composition containing about 50 to 50 parts by mass.

On the other hand, with respect to the pressure roller 70, the pressure support roller 93 arranged on the upstream side in the transport direction of the base material 8 having the toner T covers the stainless core with, for example, silicone sponge (silicone rubber foam). It was done. The pressure support roller 93 is pressed from the inside of the endless belt 90 toward the center of the heating roller 80 with a constant load. However, the pressure support roller 93
Is formed of a material softer than the coating layer 82 of the heating roller 80, the sponge layer of the pressure support roller 93 is deformed, and the heating roller 80 is hardly distorted.

The heating roller 80 is rotationally driven at an appropriate peripheral speed by a motor (not shown), and this rotation causes the endless belt 90 to be driven to rotate at substantially the same speed.

The fixing device used in the present invention may be provided with a cleaning mechanism if necessary. In this case, as a method of supplying the silicone oil to the upper roller (heating roller) of the fixing section, 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 amount at the time of use, those having a viscosity at 20 ° C. of 1 to 100 Pa · s are preferably used.

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

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

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

Here, the supply amount of the silicone oil is the transfer paper (A4) to the fixing device (between rollers) heated to a predetermined temperature.
It is calculated by continuously passing 100 sheets of white paper of a size) and measuring the mass change (Δw) of the fixing device before and after passing the paper (Δw / 100).

[0241]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these embodiments.

Example 1 << Preparation of Toner and Developer >> (Preparation of Latex) [Preparation of Latex 1HML] <1: Preparation of Core Particles (First Stage Polymerization)> Stirrer, temperature sensor, cooling tube, nitrogen introduction 5000m with equipment attached
In a separable flask of 1, the anionic surfactant A
_{(C 10 H 21 (OCH 2} CH 2) 2 OSO 4 Na) 7.08g
Was charged in 3010 g of ion-exchanged water, and a surfactant solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring rate of 230 rpm under a nitrogen stream.

To this surfactant solution, 9.2 g of a polymerization initiator (potassium persulfate: KPS) was added 200 g of ion-exchanged water.
Was added to the initiator solution and the temperature was raised to 75 ° C., and then 70.1 g of styrene and 1-n-butyl acrylate were added.
A monomer mixture solution consisting of 9.9 g and methacrylic acid 10.9 g was added dropwise over 1 hour, and this system was heated at 75 ° C. for 2 hours with stirring to perform polymerization (first stage polymerization), A latex (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 was added.
A monomer mixture consisting of 5.6 g, n-butyl acrylate 30.0 g, methacrylic acid 6.4 g, and n-octyl-3-mercaptopropionic acid ester 5.6 g was mixed with 72. 0 g was added, heated at 80 ° C. and dissolved to prepare a monomer solution 1. Then, 1.6 g of the above-mentioned 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 liquid of core particles, is added in terms of solid content, and then a mechanical disperser having a circulation path "CLEARMIX (CLEARM
IX) ”(manufactured by M Technique Co., Ltd.), the above-prepared monomer solution 1 was mixed and dispersed to prepare an emulsion containing emulsion particles having a uniform dispersed particle diameter (284 nm).

Then, a polymerization initiator (KP
S) 5.1 g of an initiator solution dissolved in 240 ml of ion-exchanged water and 750 ml of ion-exchanged water were added, and the system was heated and stirred at 80 ° C. for 3 hours to perform polymerization (second-stage polymerization). , Latex (dispersion liquid of composite resin particles having a structure in which the surface of resin particles made of a high molecular weight resin is coated with an intermediate molecular weight resin) was obtained. This is latex (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 under the temperature condition of 80 ° C., 300 g of styrene, n
-Butyl acrylate 95 g, methacrylic acid 15.3
A monomer mixture solution consisting of 10.4 g of g, n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C., and a latex (a central portion made of a high molecular weight resin, an intermediate layer made of an intermediate molecular weight resin, A dispersion liquid of composite resin particles having an outer layer made of a low molecular weight resin and containing the exemplified compound 19 as a release agent in the intermediate layer was obtained. This latex is called latex 1HML.

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

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

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

(Preparation of Toner) [Preparation of Toner Particles] <Preparation of Toner Particles 1 to 9: Present Invention> 59.0 g of anionic surfactant A was dissolved in 1600 ml of ion-exchanged water with stirring. While stirring this solution, carbon black "Regal 330" (manufactured by Cabot) 420.0
By gradually adding g, and then performing a dispersion treatment using "CLEARMIX" (manufactured by M Technique Co., Ltd.),
Dispersion liquid of colorant particles (hereinafter referred to as colorant dispersion liquid 1).
Was prepared. The particle size of the colorant particles in this colorant dispersion 1 was measured by an electrophoretic light scattering photometer "ELS-800".
When measured using (manufactured by Otsuka Electronics Co., Ltd.), the mass average particle diameter was 98 nm.

The latex 1HML prepared above was mixed with 42
0.7g (as solid content) and 900g of deionized water
And 166 g of Colorant Dispersion Liquid 1 were placed in a reaction vessel (four-necked 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 sodium hydroxide aqueous solution was added to this solution to adjust the pH to 9.0.

Then, magnesium chloride hexahydrate 12.
An aqueous solution prepared by dissolving 1 g in 1000 ml of ion-exchanged water,
The mixture was added with stirring at 30 ° C. for 10 minutes. After standing for 3 minutes, the temperature starts to rise, and this aqueous solution is used for 9 minutes over 9 minutes.
The temperature was raised to 0 ° C. (heating rate: 10 ° C./min). In that state, the particle size of the associated particles was measured with a “Coulter counter TA-II”, and when the number average particle size reached 5.5 μm, 80.4 g of sodium chloride was added to 1000 parts of ion-exchanged water.
Add an aqueous solution dissolved in ml to stop particle growth,
Further, as the aging treatment, fusion was continued by heating and stirring at a liquid temperature of 85 ° C. for 2 hours. afterwards,
After cooling to 30 ° C. under the condition of 8 ° C./minute, 20 μl of each fragrance 1 and 10 μl of each fragrance 2 were added as shown in Table 1. Then, hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped. The associated particles produced were filtered through a Nutsche, washed repeatedly with ion-exchanged water at 45 ° C., various flavors shown in Table 1 were poured onto the Nutche, filtered, dried with warm air at 40 ° C., and then hydrophobic. Add 10 parts by mass of silica 0.8 parts by mass and hydrophobic titanium oxide 1.0 parts by mass
Toner particles 1 to 21
Was prepared.

[0253]

[Table 1]

[Measurement of Odor Space of Each Toner] According to the method described below, each cos θ in the odor spaces of the toners 1 to 21 prepared above was measured.

As a measurement sample, each of the toners prepared above was used.
1 g is placed in a 2 liter sample bag made of polyethylene terephthalate. After filling with nitrogen gas, the sample bag is heated on a hot plate at 160 ° C. for 30 seconds.

<Preparation of Standard Sample> Standard sample for styrene odor: 0.2 ml of styrene saturated gas was placed in a 2 liter sample bag and diluted with nitrogen gas.

Standard sample for n-butyl acrylate odor: 2
0.2 ml of n-butyl acrylate saturated gas is placed in a liter sample bag and diluted with nitrogen gas.

Standard sample for mercaptocarboxylic acid ester odor: n-octyl-3-mercaptopropionic acid ester is used as a standard sample. A 2-liter sample bag was charged with 0.5 ml of n-octyl-3-mercaptopropionate saturated gas, diluted with nitrogen gas, and left for 1 hour.

<Measurement conditions> Measurement device: Odor identification device FF-1 (manufactured by Shimadzu Corporation) Sensor room temperature: 60 ° C Sampling flow rate: 165 ml / min Pre-sampling time: 10 seconds Sampling time: 45 seconds Collection tube temperature: 40 ° C. Dry purge temperature: 40 ° C., flow rate: 500 ml / min, time: 45 seconds Desorption collection tube temperature: 220 ° C., time: 90 seconds, flow rate: 20 ml
/ Min. Number of times of measurement per sample: 5 times or more, each measurement result obtained is shown in Table 2.

[0260]

[Table 2]

(Preparation of Developer) As the developer, a silicone-coated carrier having a volume average particle diameter of 60 μm was used, which was mixed with each toner so that the toner concentration was 6%.

<< Evaluation of Image Formation and Odor >> As an electrophotographic apparatus for evaluation of (image formation), a digital copying machine (corona charging, laser exposure, reversal development, electrostatic transfer, etc.) having the image forming process shown in FIG. (Having a nail separation), a photoreceptor and each developer were mounted and evaluated.

The above digital copying machine was evaluated under the following conditions. <Charging conditions> Charger: Scorotron charger, initial charging potential of -750
V exposure condition: set to an exposure amount that makes the exposed portion potential −50 V Development condition: DC bias; −550 V transfer pole; corona charging system <Fixing device> As the fixing device, the endless belt type fixing device shown in FIG. 5 is used. Was used.

The fixing device comprises a heating roller 80 containing a heating member 75, an endless belt 90 arranged so as to be in pressure contact with the heating roller 80, a pressure roller 70 for stretching the endless belt 90, and two rollers. Support rollers 91 and 92, and a pressure support roller 93 that presses the endless belt 90 against the heating roller 80 to form a nip portion.

The metal core 81 of the heating roller 80 is an iron cylinder having an outer diameter of 63 mm and an inner diameter of 60 mm, and the coating layer 82 has a rubber hardness of 45 ° (JIS-A) HTV (Hi).
ghTemperature Vulcanizati
on) Silicone rubber is formed to have a thickness of 1 mm, and the surface layer 71 is further formed with an RTV (RoomT) of 20 μm in thickness.
(Emperature Vulcanization)
It was formed by dip-coating silicone rubber. Also,
A halogen lamp having an output of 550 W is fixedly supported as a heating member 75 inside the cored bar 81. Further, a temperature sensor 86 was installed close to the surface of the heating roller 80 to adjust the surface temperature of the heating roller 80 to 165 ° C.

The endless belt 90 has a thickness of 75 μm.
Then, the RTV silicone rubber is used as the surface layer 94 on the polyimide film base material having a circumference of 204 mm to a thickness of 10
Coated with 0 μm. The endless belt 90 was stretched around the pressure roller 70 and the pressure support rollers 91 and 92 with a tension of 200N. The pressure roller 70 and the support rollers 91 and 92 are made of stainless steel, and their diameters are 23 mm, 20 mm, and 20 mm, respectively. Of these, the pressure roller 70 was pressed toward the center of the heating roller 80 with a load of 300N.

The pressure support roller 93 has a diameter of 13 mm.
The stainless core is coated with silicone sponge (silicone rubber foam) to a thickness of 5 mm.

The fixing device is not equipped with a cleaning mechanism and a silicone oil supply mechanism.

<Development conditions> Each of the toners was loaded in the above apparatus, the linear velocity was 420 mm / sec, the fixing temperature was 165 ° C., and the fixing amount of each toner amount was 30 times continuously under the conditions shown in Table 3.
Output operation for 1 minute was performed.

(Evaluation of Odor) <Evaluation Conditions> The electrophotographic apparatus produced as described above has an area of 19.
It is installed in the center of a closed room with a height of 8 m ² and a height of 3.8 m (space volume: 75.2 m ³ ), and 10 test subjects are placed around it, and continuous operation for 30 minutes is continuously performed under the above conditions. Then, the alpha wave and the Kraepelin test were performed by the method described below.

<Measurement of Alpha Wave> As an alpha wave as an index of relaxation, an electroencephalogram of 8 to 13 Hz appearing around the occipital region of each subject was measured after a continuous fixing process for a total of 30 minutes.

<Kraepelin test> The Kraepelin test is called "continuous first addition work" in which single digit numbers are added, and is most commonly performed as a mental work load test for evaluating work efficiency. It is a test.

Specifically, under the test environment, the Kraepelin test was conducted before the fixing treatment and after the continuous fixing treatment for 30 minutes, and the average value of each of 10 test subjects was obtained.

The addition work progress rate before the fixing process, which is the standard, was 61%. Table 3 shows the measurement results obtained as described above.

[0275]

[Table 3]

As is clear from Table 3, the toner produced through the step of forming particles in the aqueous medium, the perfume processing step and the drying step according to the present invention is used, and the odor defined in claim 2 or 3 is further used. The level according to the present invention in which the toner located in the space was used to fix the toner in the range of 4 to 158 g per minute as the toner mass, the alpha wave appearance ratio of each subject was high and the Kraepelin test was performed. We were able to confirm that the work efficiency was high.

Example 2 Using the toners 1 to 21 prepared in Example 1, the endless belt system was used instead of the heating roll system shown in FIGS. 3 and 4 as the fixing system of the electrophotographic apparatus. In the same manner, the continuous images were output, and according to the method described in Example 1, the alpha wave was measured by the subject and the Kraepelin test was performed. As a result, similar to the result of Example 1,
By using the toner according to the present invention, good results could be confirmed even in the heating roller system.

[0278]

According to the present invention, the odor produced by image forming apparatuses such as copiers and printers, which are becoming more and more popular recently, is accurately evaluated and designed, and the odor caused by the toner is suppressed during toner fixing. By using a toner that can emit a odor (fragrance) that is comfortable for humans, the appearance ratio of alpha waves can be increased and the working efficiency can be improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a vector of a toner odor along with a vector of a standard substance.

FIG. 2 is a schematic configuration diagram of an image forming apparatus showing an embodiment of the present invention.

FIG. 3 is a schematic sectional view showing an example of a heating roller type fixing device used in the electrophotographic apparatus according to the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of a heating roller type fixing device used in the electrophotographic apparatus according to the present invention.

FIG. 5 is a schematic sectional view showing an example of an endless belt type fixing device used in the electrophotographic apparatus according to the present invention.

[Explanation of symbols]

1 Semiconductor laser light source 4 photoconductor 5 charger 6 developer 7 Transfer device 8 base materials 10 Fixing device 11 Cleaning device 12 Pre-charge exposure (PCL) 13 Cleaning blade 70 Pressure roller 71, 85, 94 surface layer 75, 75 'heating member 80 heating roller 81, 83 core metal 82, 84 coating layer 86,86 'Temperature sensor 90 endless belt 91, 92 Support roller 93 Pressure support roller T undeveloped toner image T'Fixed toner image

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 381 (72) Inventor Shiro Hirano 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica Co., Ltd. F-term within company ( Reference) 2H005 AA01 AA08 AB06 AB09 CA04 CA30 EA10 2H033 AA00 BA11 BA58 BB03 BB05 BB06 BB13 BB14 BB15 BB28 BB34 CA36

Claims (3)

[Claims] 1. A recording sheet, comprising: an image bearing member on the surface of which an electrostatic latent image is formed by an electrostatic potential difference; and a developing device for adhering toner to the electrostatic latent image to form a toner image. In an electrophotographic apparatus that heats and presses the toner image transferred onto the toner to fix the toner image, the toner is manufactured through a step of forming particles in an aqueous medium, a perfume processing step, and a drying step. An electrophotographic apparatus characterized by fixing 4 to 158 g per minute. 2. The toner has a cos θ of 0.990 to 0.998 for a styrene odor and a cos θ of 0.986 to 0.9 for an n-butyl acrylate in an odor space formed of styrene and n-butyl acrylate.
2. The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus is at 94 and has a strength of 1.8 to 2.6. 3. The toner has a cos θ of 0.990 to 0.998 for a styrene odor in an odor space formed of styrene and a mercapto carboxylic acid ester, and a cos θ of 0.991 to 0 for a mercapto carboxylic acid ester odor. .999, and its strength is 1.8-
The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus is 2.6.