JP2001183869A - Polymerized toner and method for producing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymerized toner excellent in environmental characteristics as well as in blocking resistance and durability while retaining good fixability. SOLUTION: A monomer composition containing at least a polymerizable monomer and a wax composition is suspension-polymerized in an aqueous medium containing a slightly water-soluble inorganic compound and a surfactant to produce the objective polymerized toner. (1) The wax composition contains at least an ester wax formed from a 6-40C carboxylic acid compound. (2) At least a 6-40C carboxylic acid compound (salt) is used as the surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerized toner used for a recording method utilizing an electrophotographic method, an electrostatic recording method, a toner jet recording method and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat.
Numerous methods are known as described in Japanese Patent Publication No. 297691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, but generally, various methods are used by utilizing a photoconductive substance. Forming an electrical latent image on the photoreceptor, developing the latent image with toner, and transferring the toner image to a transfer material such as paper using direct or indirect means as necessary. The toner is fixed by heat, pressure, solvent vapor, or the like to obtain a printed material, and the untransferred toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

An example of a general method of forming a full-color image will be described below. A photosensitive member (electrostatic latent image carrier) of a photosensitive drum is uniformly charged by a primary charger and converted to a magenta image signal of a document. Then, an image is exposed with the laser beam modulated by the laser beam, an electrostatic latent image is formed on the photosensitive drum, and the electrostatic latent image is developed by a magenta developing device having magenta toner, thereby forming a magenta toner image. Next, the magenta toner image developed on the photosensitive drum by the transfer charger is transferred to the transferred transfer material by using a direct or indirect means. Specifically, using four photoconductors and a belt-shaped transfer member, an electrostatic latent image formed on each photoconductor is developed using cyan, magenta, yellow, and black toners. After transferring the transfer material between the straight passes and transferring it between straight passes, the transfer material is wound around the surface of the transfer body facing the photoreceptor by electrostatic force or mechanical action such as a gripper. Is generally used four times.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a static eliminator, cleaned by a cleaning unit, and charged again by a primary charger. The cyan toner image is formed and the cyan toner image is transferred to the transfer material on which the magenta toner image has been transferred. Then, the yellow toner image and the black color image are sequentially transferred to transfer the four color toner images to the transfer material. . A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

In recent years, such an apparatus is not only a copy machine for office work for copying an original document, but also a laser beam printer (LBP) as an output of a computer or a personal copy (PC) for individuals. Started to be used in the field.

In addition to the fields represented by LBP and PC, the development of plain paper facsimile machines using a basic engine is also rapidly developing.

For this reason, smaller, lighter, faster, higher image quality, and higher reliability have been strictly pursued, and machines have been constructed with simpler elements in various respects. . As a result, the performance required of the toner becomes higher, and if the performance of the toner cannot be improved, a better machine cannot be realized. In recent years, demand for color copying has rapidly increased in accordance with various needs for copying. In order to copy original color images more faithfully, higher image quality, higher resolution, etc. without image defects are desired. I have.

From these viewpoints, the toner used in the color image forming method needs to have good meltability and color mixing when heated, and has a low softening point and a low melt viscosity. It is preferable to use a toner having a high sharp melt property.

That is, by using such a sharp melt toner, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained at a higher speed.

However, such a color toner having a high sharp melt property generally has a high affinity with a fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing device in a color image forming apparatus, since magenta, cyan, yellow, and black toner layers are formed on a transfer material, offset tends to occur particularly due to an increase in toner layer thickness. It is in.

Conventionally, for the purpose of preventing the toner from adhering to the surface of the fixing roller, for example, a method has been proposed in which a releasing agent such as low molecular weight polyethylene or low molecular weight polypropylene is added to the toner.

Techniques for incorporating wax as a release agent in a toner are disclosed in, for example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 52-3305, and Japanese Patent Application Laid-Open No. 57-52574. .

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27
3554, JP-A-61-94062, JP-A-61-138259, JP-A-60-25236
No. 1, Japanese Unexamined Patent Publication No. 60-252360, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 0-217366 discloses a technique for containing waxes.

However, in the case of a black toner, although a release agent having relatively high crystallinity represented by polyethylene wax or polypropylene wax can be used to improve high-temperature offset resistance during fixing, a full-color toner cannot be used. However, because of the crystallinity of the release agent, the transparency of an OHP toner image is significantly impaired when output.
Further, it is relatively difficult to uniformly disperse such a highly crystalline release agent in the toner, and it is not easy to achieve high image quality and high durability with such a toner having a non-uniform material dispersion. Absent. In addition, the toner may be exposed to heat due to a rise in the temperature of the inside of a copying machine or the like, or the wax may migrate to the surface of the toner when the toner is left for a long time to further deteriorate the developability. Furthermore, if there is an exposed portion of the wax on the toner surface, the blocking resistance is deteriorated,
Fusion tends to occur due to mechanical stress between the toner and the carrier, between the sleeve and the developer regulating member, or between the photosensitive member and the cleaner portion, and the durability tends to be significantly reduced.

It has been pointed out that such various problems can be solved by a suspension polymerization toner, and the following production method has been proposed as a specific production method. (1) JP-A-56-130762 discloses that a toner is synthesized by a suspension polymerization method using an anionic surfactant and tricalcium phosphate as a dispersion stabilizer during suspension. I have. (2) JP-A-05-66610 discloses that an anionic surfactant selected from an alkyl sulfate, an alkyl sulfonate, an alkylbenzene sulfonate or an alkyl carboxylate and a poorly water-soluble inorganic compound are suspended. It describes that a toner is synthesized by a suspension polymerization method using a dispersion stabilizer.

In these suspension polymerization methods, a monomer composition comprising a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a cross-linking agent, a charge control agent, and other additives) is used.
The polymerization reaction is performed while dispersing using a suitable stirrer in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer to obtain toner particles having a desired particle size.

In this suspension polymerization method, since a droplet of the monomer composition is formed in a dispersion medium having a large polarity such as water, the component having a polar group contained in the monomer composition is an aqueous phase. A so-called core / shell structure in which a non-polar component does not easily exist in the surface layer portion, which is likely to be present in the surface layer portion at the interface with, can be formed. In other words, the toner produced by the polymerization method completely encapsulates the wax component, which is a release agent, so that the effect of the wax on the toner surface is completely suppressed while maintaining the low-temperature fixing property and the high-temperature offset resistance inside the toner. To enable efficient toner design. Further, by using a surfactant as the dispersion stabilizer, the particle size distribution of the toner can be adjusted relatively arbitrarily. However, since a poorly water-soluble inorganic compound such as tricalcium phosphate is used stably under alkaline conditions, a relatively high pH condition is required during the production of the toner.

By incorporating a special wax into the core of the polymerized toner thus obtained, it is possible to achieve high image quality and drastic size reduction of the image forming apparatus while maintaining blocking resistance and high durability. There is.

Here, a special wax is disclosed in
In JP-A-7-98511, 3 represented by the following formula:
A polyfunctional polyester compound having a quaternary or / and quaternary carbon and obtained from a difunctional or higher functional alcohol compound or carboxylic acid compound is disclosed.

[0021]

Embedded image [In the formula, A represents a carbon atom, an alicyclic group or an aromatic group,
R ₁ and R ₂ are the same or different groups and have 1 to 1 carbon atoms.
Shows the 35 organic group, Y ₁ and Y ₂ are the same or different groups, a hydrogen atom, a halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom and may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. However, when A represents a carbon atom and either Y ₁ or Y ₂ represents an organic group, m and n each represent an integer of 1 or more; A represents a carbon atom, and Y ₁ and Y ₂ When both represent an organic group, one of m or n represents an integer of at least 1; and when A is an aromatic group having Y ₁ and Y ₂ , m and n represent zero or an integer of 1 or more; When A represents an alicyclic group having Y ₁ and Y ₂ and m and n are zero, at least one of Y _{1 and} Y ₂ represents at least an organic group. ]

This type of wax greatly improves the low-temperature fixability and the offset resistance of the toner, and has excellent transparency when used in a color toner because of its low crystallinity, so that a high-quality full-color OHP can be obtained. .

However, the above-mentioned wax has a plurality of ester bonds, and is easily hydrolyzed under a relatively high pH condition, and a monoester or a simple alcohol compound is generated as an equilibrium product. Therefore, when producing a polymerized toner under relatively high pH conditions using the above wax, hydrolysis of the wax occurs during polymerization, the wax has a low molecular weight, as a result,
The blocking resistance and durability of the resulting polymerized toner are reduced. Furthermore, the hydrolysis equilibrium is greatly shifted even if the production conditions are slightly changed, so that it is difficult to strictly adjust the effect of the ester wax by merely adjusting the amount of the wax added.

[0024]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerized toner which is excellent in blocking resistance and durability as well as environmental characteristics while maintaining good fixing properties, and a method for producing the same. It is in.

It is another object of the present invention to provide a method for producing a polymerized toner capable of obtaining a color toner exhibiting good OHP transparency.

It is a further object of the present invention to provide a polymerized toner exhibiting excellent performance in a contact developing method using a cleaner-less method, and a method for producing the same.

[0027]

The present invention relates to an aqueous medium containing a poorly water-soluble inorganic compound and a surfactant.
A method for producing a polymerized toner in which a toner is obtained by suspension polymerizing a monomer composition containing at least a polymerizable monomer and a wax composition, wherein the wax composition has at least 6 to 40 carbon atoms. Contains an ester wax composed of a carboxylic acid compound. At least a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) is used as the surfactant. The present invention relates to a method for producing a polymerized toner, characterized by satisfying the following.

Further, the present invention comprises at least a binder resin, a colorant and a wax composition, and the wax composition contains at least an ester wax. The following conditions are satisfied. It is composed of 40 carboxylic acid compounds. The polymerized toner contains a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) in an amount of 30 to 3000 based on the mass of the toner.
ppm. Satisfies the following.

Further, the present invention provides a method of suspension polymerizing a monomer composition containing at least a polymerizable monomer, a colorant and a wax composition in an aqueous medium containing a poorly water-soluble inorganic compound and a surfactant. Wherein the wax composition contains at least an ester wax composed of a carboxylic acid compound having 6 to 40 carbon atoms. 30 to 3000 ppm of a carboxylic acid compound (including a salt) having at least 6 to 40 carbon atoms based on the mass of the toner
contains. It is manufactured using at least a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) as the surfactant.
Which is a polymerized toner.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The present inventors have paid attention to the fact that the hydrolysis reaction of the ester bond is a reversible equilibrium reaction, and as a result of intensive studies, as a result, a specific carboxylic acid compound (including a salt) was produced during the production of the polymerized toner. By using it as a surfactant and by using it as a dispersion stabilizer of the monomer composition in combination with the poorly water-soluble inorganic compound, hydrolysis of the ester wax during polymerization is suppressed, and the fixability of the toner is not impaired. It has been found that significant improvements in blocking resistance and durability can be achieved.
This is

[0032]

Embedded image By increasing the concentration of RCOOM on the right side and shifting the chemical equilibrium to the left to suppress hydrolysis of the ester wax, it is possible to incorporate it in the polymerized toner while maintaining the properties of the ester wax used as much as possible. It was done.

Representative examples of preferred ester waxes used in the present invention include the following.・ Ester wax obtained from monoalcohol having 8 or more carbon atoms and monocarboxylic acid having 6 to 40 carbon atoms ・ Montan wax represented by the following structural formula

[0034]

Embedded image [Wherein, R represents a hydrocarbon group having 28 to 32 carbon atoms;
Represents an integer. A polyfunctional polyester compound represented by the following structural formula

[0035]

Embedded image [In the formula, A represents a carbon atom, an alicyclic group or an aromatic group,
R ₁ and R ₂ are the same or different groups and have 1 to 1 carbon atoms.
Shows the 35 organic group, Y ₁ and Y ₂ are the same or different groups, a hydrogen atom, a halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom and may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. However, when A represents a carbon atom and either Y ₁ or Y ₂ represents an organic group, m and n each represent an integer of 1 or more; A represents a carbon atom, and Y ₁ and Y ₂ When both represent an organic group, one of m or n represents an integer of at least 1; and when A is an aromatic group having Y ₁ and Y ₂ , m and n represent zero or an integer of 1 or more; When A represents an alicyclic group having Y ₁ and Y ₂ and m and n are zero, at least one of Y _{1 and} Y ₂ represents at least an organic group. The alcohol component of the ester is glycerin and / or
Or a higher fatty acid ester which is diglycerin and whose acid component is a higher fatty acid having 10 to 40 carbon atoms in an acyl group.

In particular, it is preferable that the alcohol compound constituting the ester wax is a monoalcohol, or the carboxylic acid compound constituting the ester wax is a monocarboxylic acid, and the ester wax composed of a monoalcohol and a monocarboxylic acid is preferred. More preferred. 1
When two or more ester bonds are present in the molecule, the products of the hydrolysis equilibrium are various, and the physical properties such as the softening point of the wax contained in the toner are distributed. Adjustment becomes difficult. In addition, when the number of ester bonds in the wax molecule increases, the polarity of the wax increases, so that the wax tends to be present on the surface of the suspended particles during polymerization of the monomer composition. , The amount of wax present increases, and the blocking resistance tends to decrease. Further, the charge amount under high humidity tends to decrease, which adversely affects the durability.

In the above-mentioned ester wax, the softening point of the wax itself increases when the number of carbon atoms of the carboxylic acid component increases, so that the low-temperature fixability of the toner containing the ester wax tends to decrease. ,
Conversely, when the amount decreases, the so-called plasticity effect tends to lower the high-temperature offset resistance of the toner. Therefore, as the carbon number of the carboxylic acid constituting the ester wax,
Generally, those having 6 to 40 are preferably used.

In order to maintain the performance of the ester wax, it is important to use a carboxylic acid compound having 6 to 40 carbon atoms as a surfactant during the production of the polymerized toner. As described above, this is necessary in order to prevent the ester wax from being reduced in molecular weight due to hydrolysis at the time of polymerization and to suppress a decrease in blocking resistance and durability of the toner.

If the carboxylic acid compound used has less than 6 carbon atoms, the ester wax cannot be sufficiently reduced in molecular weight, and it is difficult to suppress the deterioration of the blocking resistance and durability of the toner. On the other hand, if the number of carbon atoms of the carboxylic acid compound used exceeds 40, the molecular weight of the equilibrium product becomes too large, thus impairing the property of the ester wax having a low-temperature fixing property as described above. .

Further, as the carboxylic acid compound, it is even more preferable to use the carboxylic acid compound constituting the ester wax contained in the toner. this is,
In the hydrolysis equilibrium, since the transesterification product of the raw material ester wax and the carboxylic acid used as the surfactant is the same as the raw material ester wax, the structure of the ester wax added during polymerization is unchanged. Is included in the toner, and the effect of improving the fixability of the ester wax is maximized.

A major feature of the toner according to the present invention is that an alcohol compound or a carboxylic acid compound (including a salt) constituting the ester wax contained in the toner.
From 30 to 3000 ppm based on the mass of the toner.

In general, the charge amount of the toner tends to increase under low humidity and tends to decrease under high humidity. The charge amount of the toner greatly depends on the content of the polar substance in the toner and the water absorption thereof. The charge quantity decreases when the content of the polar substance is large, and conversely, the charge quantity decreases when the content of the polar substance is small. It is known that the amount tends to be higher. Therefore, by appropriately selecting the amount of the surfactant used during the polymerization and the washing conditions of the toner after the completion of the polymerization reaction, the polar substance in the toner (that is, in the present invention, the ester wax contained in the toner is constituted) By adjusting the content of the alcohol compound or carboxylic acid compound) to an appropriate range, the charge amount can be stabilized in all environments from high humidity to low humidity, and a high-quality image can be obtained for a long time. Can be obtained.

At this time, the amount of the alcohol compound or carboxylic acid compound contained in the toner is 30
If the amount is less than ppm, it is difficult to suppress an increase in the charge amount of the toner under low humidity, and the toner adheres strongly to a sleeve, a carrier, or the like, and is likely to cause fusion or the like, which is not preferable. On the other hand, the amount of the alcohol compound or carboxylic acid compound contained in the toner is 3000
When the amount exceeds ppm, it is difficult to suppress a decrease in the charge amount of the toner under high humidity, and it is easy to cause a decrease in durability such as fog, deterioration of image quality, or toner scattering, which is not preferable.

Next, a method for producing a polymerized toner according to the present invention will be described. Specifically, for example, a wax, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the monomer, and the monomer is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. The composition is dispersed in an aqueous phase containing a dispersion stabilizer composed of a poorly water-soluble inorganic compound and a surfactant using a conventional stirrer, homomixer, homogenizer, or the like. Preferably, the stirring speed and time are adjusted so that the droplets of the monomer composition have the desired size of the toner particles, and the granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction, and further for the purpose of further improving the durability properties, in order to remove unreacted polymerizable monomers and by-products, the second half of the reaction,
Alternatively, a part of the aqueous medium may be distilled off after the completion of the reaction. After the reaction, the generated toner particles are collected by washing and filtration, and dried. At this time, by appropriately selecting the amount of the surfactant in the aqueous phase and the conditions of the washing step after the completion of the reaction, the amount of the alcohol compound or the carboxylic acid compound contained in the toner is reduced to 30 to 3000 ppm based on the mass of the toner. It is good to adjust. In this method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

The surfactant may be added at the same time as the monomer composition to the aqueous phase containing the dispersion stabilizer consisting of the poorly water-soluble inorganic compound alone, or may be added after the monomer composition. Then, they may be dispersed.

Examples of the polymerizable monomer for the polymerized toner according to the present invention include styrene-based monomers such as styrene, o (m-, p-)-methylstyrene and m (p-)-ethylstyrene. ; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
Butyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (Meth) acrylate monomers such as diethylaminoethyl (meth) acrylate; butadiene,
Monomers such as isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide are preferably used. These can be used alone or generally in the published Polymer Handbook, 2nd Edition-P139-192 (John Wil).
eye & Sons) and the theoretical glass transition temperature (T
The monomer is appropriately mixed and used so that g) indicates 40 to 75 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems arise in terms of the storage stability of the toner and the durability stability of the developer. In some cases, the color mixture of each color toner is insufficient, resulting in poor color reproducibility.
The transparency of the HP image is significantly reduced, which is not preferable from the viewpoint of high image quality. At this time, if a monomer having two or more polymerizable functional groups in one molecule, such as divinylbenzene, is contained, an appropriate network is formed in the toner, and the fixing property and the durability are further improved. It becomes possible.

Examples of the polymerization initiator used for polymerization in an aqueous medium in the present invention include, for example, 2,2′-azobis-
(2,4-dimethylvaleronitrile), 2,2′-azobisibutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4
Azo-based polymerization initiators such as -methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl A peroxide-based polymerization initiator such as peroxide is used.

The amount of the polymerization initiator to be added varies depending on the desired degree of polymerization, but generally ranges from 0.5 to 2 parts by weight per monomer.
0 mass% is added and used. Although the type of the initiator slightly varies depending on the polymerization method, it is used alone or in combination with reference to the 10-hour half-life temperature.

In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like may be further added and used.

The poorly water-soluble inorganic compound dispersant used in the method for producing a polymerized toner according to the present invention includes, for example,
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ,
Magnetic materials, ferrites and the like can be mentioned. These dispersants are
It is preferable to use 0.2 to 10 parts by mass based on 100 parts by mass of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound is formed under high-speed stirring in a dispersion medium. Can also. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

When the toner is produced by the polymerization method of the present invention, it is necessary to pay attention to the polymerization inhibitory property and aqueous phase transfer property of the colorant, and it is preferable to use a surface modification, for example, a substance having no polymerization inhibition. It is better to perform a hydrophobic treatment. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the same treatment as the above dye.

The coloring agents used in the toner according to the present invention include the following yellow coloring agents, magenta coloring agents and cyan coloring agents. Carbon blacks, magnetic materials, titanium black or mixtures thereof as black coloring agents are listed below. Alternatively, a mixture of the following yellow colorant / magenta colorant / cyan colorant and adjusted to black is used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
An azo metal complex, a methine compound, a compound represented by an allylamide compound, or the like is used. Specifically, C.I. I.
Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 and the like are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant is selected from the points of hue, saturation, lightness, weather resistance, OHP transparency, and dispersibility. The amount of the colorant to be added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. 1
If the amount is less than 20 parts by mass, sufficient coloring power cannot be obtained, and if the amount exceeds 20 parts by mass, the transparency of the OHP image is reduced.

Further, the toner according to the present invention uses a magnetic material as a black colorant and can be used as a magnetic toner. In this case, as a magnetic material that can be used,
Iron oxides such as magnetite, hematite, and ferrite;
Metals such as iron, cobalt, nickel or these metals aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth,
Cadnium, calcium, manganese, selenium, titanium,
Examples include alloys of metals such as tungsten and vanadium and mixtures thereof.

These magnetic materials have an average particle size of 2 μm or less,
Preferably, it is about 0.1 to 0.5 μm. The amount of the magnetic substance contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 200 parts by mass, per 100 parts by mass of the resin.
It is 150 parts by mass. Also, 795.8 kA / m (10
000 Oersted), the coercive force (H
c) 1.59-23.9 kA / m (20-30 Oersted), saturation magnetization (σs) 50-200 Am ² / kg,
A magnetic material having a residual magnetization (σr) of ^{2 to} 20 Am ² / kg is preferable.

As the charge control agent used in the toner according to the present invention, a known charge control agent can be used. In particular, a charge control agent which has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and having substantially no solubilized substance in an aqueous dispersion medium is particularly preferable. Specific examples of the compound include a metal compound of an aromatic carboxylic acid such as salicylic acid, naphthoic acid and dicarboxylic acid and a metal salt or metal complex of an azo dye or an azo pigment, a sulfonic acid or a carboxylic acid as a negative charge control agent. Examples thereof include a polymer compound having an acid group in a side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, an imidazole compound and the like. The charge control agent is preferably used in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the resin. However, in the present invention, the addition of a charge control agent is not essential. When a two-component developing method is used, triboelectric charging with a carrier is used, and when a one-component developing method is used, developer regulation ( It is not always necessary to include a charge control agent in the toner particles by actively utilizing the triboelectric charging of the blade) member and the toner carrier.

The toner according to the present invention may be further used by adding a fluidity improver. The fluidity improver is not particularly limited as long as it can improve fluidity after being added to the toner particles.
For example, silica fine powder, titanium oxide fine powder, alumina fine powder, or those obtained by subjecting their surfaces to a hydrophobic treatment can be used alone or in combination of two or more.

The toner of the present invention may be used as a one-component phenomena agent, or may be used in combination with a carrier as a two-component phenomena agent.

Examples of the carrier used together with the two-component agent include those known in the art, such as iron powder, magnetite powder, ferrite powder, glass beads and magnetic powder dispersed in a resin. . These carriers may be coated on the surface with a resin or the like as necessary. Examples of the resin used in this case include a fluorine-containing resin, a phenol resin, a styrene resin, an acrylic resin, and a styrene-acryl copolymer. , Silicone resin and the like.
These coating resins may be used alone or in combination of two or more. When the mixing ratio between the toner and the carrier is 1 to 15% by mass, preferably 2 to 13% by mass as the toner concentration in the developer, usually good results can be obtained.

The toner according to the present invention can be used in various image forming methods.

At this time, various charging methods can be used. For example, a direct charging method in which a charging member is brought into contact with a photoreceptor is suitably used for suppressing ozone generation. In this case, when a toner manufactured by a general pulverization method is used, if residual toner after the cleaning process adheres directly to the charging member in the subsequent process, charging failure is caused and charging unevenness occurs on an image. Therefore, the amount of the residual toner needs to be smaller and less likely to adhere as compared with corona discharge or the like in which the charging unit does not come into contact with the photoreceptor. There is a method of using a toner whose shape factors SF-1 and SF-2 are strictly specified. Here, if a polymerized toner is produced using a specific surfactant as in the method of the present invention, the shape factor S of the toner
The value of F-1 is 100 to 140 and the shape factor SF-2
Can be easily adjusted to 100 to 120, so that high transferability can be imparted to the toner, and good durability can be exhibited even when used in an image forming method using a direct charging method. Further, since the residual toner can be reduced as much as possible, a cleanerless image forming method can be used.

Here, SF-1 indicating the shape factor means, for example, 100 toner images enlarged at a magnification of 500 times using a FE-SEM (S-800) manufactured by Hitachi, Ltd., and randomly sampled. The information is transmitted through, for example, an image analyzer (Luzex II) manufactured by Nicole Corporation via an interface.
Analysis is performed by introducing I), and a value calculated by the following equation is defined as a shape factor SF-1.

[0067]

(Equation 1) [Wherein, MXLNG represents the absolute maximum length of the toner particles,
AREA indicates the projected area of the toner particles. ]

Further, the shape factor SF-2 is a value obtained by calculation according to the following equation.

[0069]

(Equation 2) [Where PER1 represents the circumference of the toner particles, and AREA
Indicates the projected area of the toner particles. ]

The shape factor SF-1 indicates the degree of roundness of the toner particles, and the shape coefficient SF-2 indicates the degree of unevenness of the toner particles.

Here, when SF-1 becomes large, it becomes far from spherical and approaches an irregular shape, so that the toner is easily crushed in the developing device, the particle size distribution fluctuates, and uniform and smooth charging of toner particles is hindered. When such a toner is used in the formation of a cleanerless image, the recoverability of the toner is reduced, and the development of the toner on the non-image portion on the photoconductor, that is, so-called fogging is likely to occur. Further, an increase in the contact area between the toner and the surface of the photoreceptor due to an increase in the contact area of the toner also leads to a decrease in the toner recoverability.

Further, when SF-2 is too large, the transfer efficiency of the toner to the transfer material is lowered, and the transfer residual toner is increased.

In particular, the above-mentioned tendency becomes apparent when a full-color image forming method for developing / transferring a plurality of toner images using an intermediate transfer member is used. In other words, in the generation of a full-color image, toner images for four colors are formed on the intermediate transfer member and then transferred collectively onto the transfer material. This is because the condition for cleaning the intermediate transfer member becomes more severe because the amount of residual toner also increases.

Further, in this case, since the transfer step is performed substantially twice, the rate of decrease in the transfer efficiency is remarkable, which causes a problem that the use efficiency of the toner is reduced. In digital full-color copiers and printers, color image originals are stored in B (blue)
Filter, G (green) filter, R (red)
After color separation using a filter, 20-70
μm dot latent image is formed, Y (yellow) toner, M
It is necessary to reproduce a multicolor image faithful to a document by using the primary color mixing action using toners of (magenta) toner, C (cyan) toner, and B (black) toner. At this time, the Y toner and the M
Since a large amount of toner, C toner, and B toner are applied according to the color information of the original or CRT, extremely high transferability is required for faithful image reproduction. Toner particles whose coefficients SF-1 and SF-2 satisfy the above conditions are preferred. The polymerized color toner obtained by the production method of the present invention can be very suitably used in a full-color image forming method using such an intermediate transfer member.

As one of the image forming methods using the toner according to the present invention, it is preferable to use a so-called contact developing method in which the surface of the photoconductor is in contact with the toner carrier.
It is more preferable to use the reversal development method. Further, the toner according to the present invention is excellent in offset resistance because of using an ester wax as an essential component, and can basically simplify the fixing device configuration because it can perform oilless fixing,
By using the cleanerless process together, the size of the apparatus can be significantly reduced.

Here, the usefulness of using the toner according to the present invention in a contact developing method using a cleanerless process will be further described.

At the contact portion between the toner carrier and the surface of the photoreceptor, that is, at the developing nip portion, considerable mechanical stress is applied to the intervening toner. Therefore, a structure that is strong in stress resistance is required for the toner, but this is inconsistent with the low-temperature fixability of the toner, and it is difficult to achieve with a general toner.

However, according to the toner manufacturing method of the present invention, an ester wax having a high effect of improving low-temperature fixability can be completely included in the toner, and the obtained toner has both stress resistance and low-temperature fixability. Therefore, it can be suitably used also in the contact developing method. In this contact developing method, a method in which an elastic roller is used as the toner carrier, a developer is coated on the surface of the elastic roller or the like, and the developer is brought into contact with the surface of the photoconductor is also used. At this time, at the time of development or at the time of blank before and after development, a bias of a DC or AC component is applied between the toner carrier and the photoreceptor, and the potential is controlled so that the residual toner on the photoreceptor can be collected during the development process. . At this time, the DC component is located between the light portion potential and the dark portion potential. In this way, by the electric field acting between the photoconductor and the elastic roller facing the photoconductor surface via the developer, the transfer residual toner is also cleaned at the same time as the development, so that the elastic roller surface or the vicinity of the surface has a potential, It is necessary to have an electric field in a narrow gap between the photosensitive member surface and the toner carrying surface. For this reason, it is also possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the medium resistance region to keep the electric field while preventing conduction with the photoreceptor surface, or to provide a thin insulating layer on the surface layer of the conductive roller. .
Further, it is also possible to adopt a configuration in which a conductive layer is provided on a conductive roller on a conductive roller on which the side facing the photoreceptor surface is covered with an insulating material, or on a side not facing the photoreceptor with an insulating sleeve. It is also possible to employ a configuration in which a rigid roller is used as the toner carrier and the photosensitive member is a flexible member such as a belt. The resistance of the developing roller as a toner carrying member is preferably in the range of 10 ² ~10 ⁹ Ω · cm.

When the surface shape of the toner carrier is set so that its surface roughness Ra (μm) is 0.2 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the developer carrying ability and the developer charging ability.
When the surface roughness Ra of the toner carrier exceeds 3.0, it becomes difficult not only to reduce the thickness of the developer layer on the toner carrier but also to improve the image quality because the chargeability of the developer is not improved. I can't hope. By setting the ratio to 3.0 or less, the ability to transport the developer on the surface of the toner carrier is suppressed, the developer layer on the toner carrier is made thinner, and the number of times of contact between the toner carrier and the developer is increased. Therefore, the chargeability of the developer is also improved, so that the image quality is synergistically improved. On the other hand, when the surface roughness Ra is 0.2
If it is smaller than this, it becomes difficult to control the amount of developer coating. Here, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness “JIS B0601”. Center line average roughness.
Specifically, a portion of 2.5 mm as a measurement length a is extracted from the roughness curve in the direction of its center line, the center line of the extracted portion is the X axis, the direction of the vertical magnification is the Y axis, and the roughness curve is y
= F (x) means a value obtained by the following equation expressed in micrometer (μm).

[0080]

(Equation 3)

In the image forming method without contact development and cleaner, the toner carrier may rotate in the same direction as the peripheral speed of the photosensitive member, or may rotate in the opposite direction. When the rotation is in the same direction, the peripheral speed of the toner carrier is preferably set to be 1.05 to 3.0 times the peripheral speed of the photoconductor.

If the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect of the toner on the photoreceptor becomes insufficient, and good image quality cannot be expected.
Further, when developing an image requiring a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient, and the image density is reduced. The higher the peripheral speed ratio, the greater the amount of toner supplied to the developing site, the more frequently the toner is attached to and detached from the latent image, and unnecessary portions are collected and added to necessary portions. Thus, an image faithful to the latent image can be obtained. Cleanerless,
In other words, from the viewpoint of development and cleaning, when there is a transfer residual toner closely adhered to the photoconductor, unnecessary toner firmly adhered to the surface of the photoconductor is rubbed with a peripheral speed difference to reduce the adhesive force, and an electric field is applied. Since the effect of collecting is important, the higher the peripheral speed ratio is, the more convenient it is to collect the residual toner. However, if the peripheral speed ratio exceeds 3.0, on the contrary, in addition to the various problems caused by the excessive charging of the toner as described above (image density reduction due to excessive toner charge-up, etc.), mechanical Deterioration of the toner due to the stress and adhesion of the toner to the toner carrier are generated and accelerated, which is not preferable.

However, in any case, the rubbing of the toner between the toner carrier and the photosensitive member is a necessary element, and the toner having high stress resistance according to the present invention is greatly welcomed.

The photoreceptor used is a-Se, C
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as ds, ZnO ₂ , OPC, and a-Si is preferable.

As the binder resin of the organic photosensitive layer in the OPC photosensitive member, polycarbonate resin, polyester resin and acrylic resin are particularly excellent in transferability and cleaning property.
This is preferable because cleaning failure, fusion of the toner to the photoconductor, and filming of the external additive hardly occur.

Next, various measuring methods in the present invention will be described.

(1) Quantification of Alcohol Compound and Carboxylic Acid Compound in Toner: The quantification of the carboxylic acid compound contained in the toner was performed as follows. 0.5 to 1.0 g of a toner sample is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kabushiki Kaisha), passed through a Soxhlet extractor, and mixed with 100 to 200 ml of a water / methanol mixed solvent as a solvent. And extracted for 12 hours. An aqueous hydrochloric acid solution was added to the obtained extract to adjust the pH of the whole solution to 5.
After removing the free carboxylate anion to 3 or less, preferably 3 or less, ether extraction is performed by a separating funnel or the like. The obtained ether-side solution is dried with sodium sulfate or the like and filtered. At this time, when the amount of the ether solution as the filtrate is large, the ether component may be reduced by distillation or the like to increase the dissolved compound concentration. Amount of carboxylic acid in ether solution obtained in this way (W _COOH g)
Is determined by gas chromatography. At that time, if the boiling point of the carboxylic acid seems to be too high, it may be determined after the silylation with a silylating agent to lower the boiling point. In the case of silylation, it is necessary to remove methanol from the extract obtained by Soxhlet extraction by distillation or the like.

At this time, the content of the carboxylic acid compound in the toner is obtained by the following equation.

Carboxylic acid compound content = (W _COOH / W
1) × 10 ⁶ (unit: ppm)

(2) Average particle size and particle size distribution of toner: The average particle size and particle size distribution of the toner
Using an A-II type or Coulter Multisizer (manufactured by Coulter) or the like, an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC) are connected. To prepare a 1% aqueous solution of NaCl. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the dispersion was treated with the Coulter Counter TA-II as an aperture.
The volume distribution and the number distribution were calculated by measuring the volume and the number of toner particles of 2 μm or more using a μm aperture. Then, a volume-based weight average particle diameter (D4) determined from the volume distribution according to the present invention was determined.

(3) Method of Measuring Friction Charge: FIG. 1 is an explanatory view of an apparatus for measuring the charge of toner. First, about 0.5 to 1.0 g of a mixture (developer) of a toner and a carrier whose frictional charge is to be measured is placed in a metal measuring container 12 having a 500-mesh screen 13 at the bottom. Do 14. At this time, the mass of the entire measurement container 12 is weighed and set as W3 (kg). Next, in the suction device 11 (at least a portion in contact with the measurement container 12 is an insulator),
The pressure of the vacuum gauge 15 is set to 2450 Pa (250 mmAq) by adjusting the air volume by suctioning from the suction port 16. In this state, suction is performed sufficiently, preferably for about 2 minutes to remove the toner by suction. The potential of the electrometer 18 at this time is set to V (volt). Here, 17 is a capacitor whose capacity is C (mF).
And In addition, the mass of the whole measurement container after the suction is weighed and W4
(Kg). At this time, the frictional charge amount of the toner (mC
/ Kg) is calculated as follows.

Amount of triboelectric charge of toner (mC / kg) = (C
× V) / (W3-W4)

(4) Method of measuring fogging of fixed image: Fogging was measured using REFLECTMETER manufactured by Tokyo Denshoku Co., Ltd.
Measured using MODEL TC-6DS. As a filter, a green filter was used for the black toner and the magenta toner, an amber light filter was used for the cyan toner, and a blue filter was used for the yellow toner. The smaller the number,
Low fog.

Fog (reflectance) (%) = Reflectance on standard paper (%) − Reflectivity of non-image portion of sample (%)

[0095]

Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited to these examples.

Production Example 1 of Polymerized Toner 1 A 0.1 M Na ₃ PO ₄ aqueous solution 5 was added to 650 g of ion-exchanged water in a two-liter four-necked flask equipped with a baffle plate.
After adding 100 g and heating to 60 ° C., the high-speed stirrer T
Using a K-type homomixer (manufactured by Tokushu Kika Kogyo), 120
The mixture was stirred at 00 rpm. 1.0M-CaCl ₂
70 g of an aqueous solution was gradually added, and 0.11 g of sodium behenate (C ₂₁ H ₄₃ COONa) (10
0 ppm) to obtain a water-based dispersion medium containing a dispersion stabilizer composed of a minute water-insoluble inorganic compound and a surfactant.

On the other hand, as dispersoids: 80 parts by mass of styrene 20 parts by mass of n-butyl acrylate 5 parts by mass of colorant (carbon black) 2 parts by mass of negative charge control agent (compound of monoazo dye and iron) Ester wax mainly composed of ester compound obtained from behenic acid (C ₂₁ H ₄₃ COONa) and behenyl alcohol (C ₂₂ H ₄₅ OH) 4 parts by mass Of the above formulation, only carbon black, iron compound of monoazo dye, and styrene were added. Lighter (Mitsui Metals)
Was used to produce a carbon black masterbatch. Next, this masterbatch and the remaining ingredients of the above formulation were heated to 60 ° C. and dissolved and dispersed to form a monomer mixture.
Further, while maintaining the temperature at 60 ° C., 8 g of an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

The above monomer composition was added to the aqueous dispersion medium prepared in the 2-liter flask of the homomixer. The mixture was stirred at 12000 rpm for 20 minutes using a TK homomixer in a nitrogen atmosphere at 60 ° C. to granulate the monomer composition. Then, while stirring with paddle stirring blades, 60 ° C
For 6 hours, and then polymerized at 80 ° C. for 8 hours.

After completion of the polymerization reaction, the reaction product is cooled, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain black polymer particles having a weight average diameter of about 7.2 μm. I got

With respect to 100 parts by mass of the obtained black polymer particles, the surface of a silica matrix having a specific surface area of 200 m ² / g by the BET method was subjected to a hydrophobic treatment with a silane coupling agent and silicone oil to give a specific surface area of 120 mm. 1.5 parts by mass of hydrophobic silica of ² / g was externally added to obtain Polymerized Toner 1.

Table 1 shows the physical properties of the polymerized toner 1 thus obtained.

Production Example 2 of Polymerized Toner Black polymer particles were obtained in the same manner as in Production Example 1 of the polymerized toner except that sodium behenate was not used as the dispersion stabilizer, but the weight average diameter was about 11.2 μm. The particle size was larger than the desired particle size, and when observed by SEM, it was confirmed that considerable particles had coalesced. Therefore, although the toner blocking test was performed, the image evaluation and printing durability test described later were not performed. .

The physical properties of the obtained black polymer particles were measured using the toner No. 1 shown in Table 1. It is shown in 2 places.

Production Examples of Polymerized Toners 3 and 4 Sodium behenate as a dispersion stabilizer was added to water in an amount of 7%.
Except for using 00 ppm or 20 ppm, the same method as in Production Example 1 of the polymerized toner was used, and the weight average diameter was about 6.2.
μm and 9.1 μm black polymer particles were obtained.

To 100 parts by mass of each of the obtained black polymer particles, 1.8 parts by mass and 1.2 parts by mass of the hydrophobic silica used in Production Example 1 of the polymerized toner were externally added, respectively. And 4 were obtained.

Table 1 shows the physical properties of the resulting polymerized toners 3 and 4.

[0107]Production Example 5 of Polymerized Toner Dodecane instead of sodium behenate as a surfactant
Sodium acid (C₁₁H _{twenty three}COONa) against water 10
0 ppm, dispersion stabilizer with poorly water-soluble inorganic compound
Method similar to that of Production Example 1 of polymerized toner except that
Gives black polymer particles having a weight average diameter of about 7.4 μm.
Was.

The hydrophobic silica used in Production Example 1 of the polymerized toner was added to 100 parts by mass of the black polymer particles thus obtained.
By external addition of 5 parts by mass, polymerized toner 5 was obtained.

Table 1 shows the physical properties of the polymerized toner 5 thus obtained.

Production Example 6 of Polymerized Toner A polymerized toner was prepared except that the wax used was changed to 4 parts by mass of a polyfunctional ester wax mainly composed of an ester wax obtained from behenic acid and glycerin (molar ratio: 3: 1). In the same manner as in Production Example 1, black polymer particles having a weight average diameter of about 7.0 μm were obtained.

To 100 parts by mass of the obtained black polymer particles, the hydrophobic silica used in Production Example 1 of the polymerized toner was added in an amount of 1.
By external addition of 5 parts by mass, a polymerized toner 6 was obtained.

Table 1 shows the physical properties of the polymerized toner 6 thus obtained.

Production Example 7 of Polymerized Toner Production Example 6 of Polymerized Toner except that the surfactant used was changed from sodium behenate to sodium dodecanoate.
Black polymer particles having a weight average diameter of about 6.6 μm were obtained in the same manner as described above.

The hydrophobic silica used in Production Example 1 of the polymerized toner was added to 100 parts by mass of the obtained black polymer particles in an amount of 1 part by mass.
By external addition of 5 parts by mass, polymerized toner 7 was obtained.

Table 1 shows the physical properties of the polymerized toner 7 thus obtained.

Production Example 8 of Polymerized Toner A weight average diameter of about 10.8 μm was obtained by the same method as in Production Example 6 of the polymerized toner except that the surfactant used was changed from sodium behenate to sodium n-pentanoate. Slightly larger black polymer particles were obtained. When observed by SEM, it was confirmed that the particles were somewhat united,
Image evaluation and printing durability test were performed.

The hydrophobic silica used in Production Example 1 of the polymerized toner was added to 100 parts by mass of the obtained black polymer particles.
By external addition, 5 parts by mass of polymerized toner 8 was obtained.

Table 1 shows the physical properties of the polymerized toner 8 thus obtained.

Production Examples of Polymerized Toners 9 to 11 I. Pigment Yellow 17,
C. I. Pigment Red 202 or C.I. I. Pigment Blue 15: 3, and the weight average diameter is determined in the same manner as in Production Example 1 of the polymerized toner except that 2 parts by mass of an aluminum compound of 2,5-di-tert-butylsalicylic acid is used as a negative charge control agent. About 7.1 μm,
Colored polymer particles of 7.0 μm and 7.2 μm were obtained.

To 100 parts by mass of the obtained colored polymer particles, 1.5 parts by mass of the hydrophobic silica used in Preparation Example 1 of the polymerized toner was externally added, and the polymerized toner 9 for yellow color and the polymerized toner for magenta color were added. Polymerized toner 10 and polymerized toner 11 for cyan color were obtained.

Table 1 shows the physical properties of the resulting polymerized toners 9 to 11.

[0122]

[Table 1]

Example 1 In the polymerized toners 1 to 11, the blocking resistance was evaluated by the following method in the state of the colored polymer particles before silica was externally added.

The colored polymer particles 10 were added to a 50 ml polycup.
g of the toner, and allowed to stand in a hot-air dryer set at 45 ° C. for one week. Then, the state of the left toner when the removed polycup was slowly rotated was visually evaluated. A: The fluidity is not impaired. B: Although the fluidity is reduced, the fluidity is gradually recovered as the cup rotates. C: Aggregates can be seen, but loosened with a needle. D: Granulation or caking so as not to be loosened even with a needle.

Table 2 shows the evaluation results.

Example 2 A polymer toner 1 and a ferrite carrier (average particle diameter 39 μm) obtained by coating a carrier core material with 0.3 part by mass of a mixture of a fluorine-based copolymer resin and a styrene-based copolymer resin were used. Was mixed so that the toner concentration in the developer was 7% to prepare a developer. Separately, prepare an electrophotographic copying machine CLC-700 (manufactured by Canon),
The oil application unit was removed from the fixing unit. Using this modified copier, in an environment of a temperature of 30 ° C./85% humidity and a temperature of 23 ° C./humidity 10%, an original document having an image area ratio of 20% is used, and only 10,000 black-and-white images can be used. A printing test was performed.

As a result, in an environment of a temperature of 30 ° C. and a humidity of 85%, the initial charge amount was −29 mC / kg → 100
-28 mC / kg after 00 sheets, initial Macbeth image density 1.
54 → 1.55 after 10,000 sheets, initial fog density 0.3
% → 0.4% after 10,000 sheets, while the initial charge amount is −32 mC / even in an environment of a temperature of 23 ° C. and a humidity of 10%.
kg → −32 mC / kg after 10,000 sheets, initial Macbeth image density 1.51 → 10000 sheets after 1.50, initial fog density 0.3% → 10000 sheets after 0.4%, which is very good in any environment. It has been stable.

After a printing test in an environment of a temperature of 23 ° C. and a humidity of 10%, the carrier surface was observed with a SEM, and no toner spent was observed.

The results of the printing durability test are summarized in Table 2.

<Examples 3 to 10, Comparative Examples 1 and 2 (No Printing Durability Test for Toner)> The same printing durability test as in Example 2 was performed using toners 3 to 11. The results are summarized in Table 2.

In Examples 8 to 10, the transparency of the OHP image of each color toner was visually evaluated. As a result, it was confirmed that the image was a good OHP image without turbidity.

[0132]

[Table 2]

<Examples 11 to 19> As an electrophotographic apparatus, a 600 dpi laser beam printer (manufactured by Canon: L
BP-860). Process speed is 65m
m / s.

For the test in the contact developing method using a cleanerless method, the cleaning rubber blade in the process cartridge was removed, the charging method of the apparatus was set to direct charging performed by contacting a rubber roller, and the applied voltage was changed to a DC component (−). 1150 V).

Next, the developing portion of the process cartridge was modified. An outline is shown in FIG. A medium-resistance rubber roller (1) made of silicone rubber in which carbon black is dispersed instead of the stainless steel sleeve that is the toner supplier
6φ, hardness ASKER C45 degree, resistance 10 ⁵ Ω · c
m) was used as the toner carrier 37 and was in contact with the photoconductor 35.
At this time, the developing nip width was set to about 2.5 mm. The rotational speed of the toner carrier is the same in the contact portion with the photoconductor, and is 150
%.

The photosensitive member used here is 30φ, 2
A 54 mm Al cylinder was used as a substrate, and layers having the following constitutions were sequentially laminated by dip coating on the substrate to prepare a photoreceptor.

(1) Conductive coating layer: Mainly composed of powder of tin oxide and titanium oxide dispersed in a phenol resin. The thickness is 15 μm. (2) Undercoat layer: mainly composed of modified nylon and copolymerized nylon. The film thickness is 0.6 μm. (3) Charge generation layer: mainly composed of a butyral resin in which a titanyl phthalocyanine pigment having absorption in a long wavelength region is dispersed. The film thickness is 0.6 μm. (4) Charge transporting layer: mainly composed of a hole transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 according to Ostwald viscosity method) at a mass ratio of 8:10. Film thickness 20 μm.

As a means for applying the toner to the toner carrier, a developing device 31 was provided with an application roller 32 made of urethane foam rubber, and was brought into contact with the toner carrier. A voltage of about -550 V is applied to the application roller. Further, a stainless steel blade 33 coated with a resin for controlling the toner coating layer on the toner carrier was attached so that the contact pressure with the toner carrier was about 20 g / cm. Further, the applied voltage at the time of development was only the DC component (−450 V).

The electrophotographic apparatus was modified and the process conditions were set as follows so as to be adapted to the modification of the process cartridge. An outline is shown in FIG.

The modified device is a roller charger 110
(Apply DC only) to uniformly charge the photoconductor 109.

After charging, an image portion is exposed by a laser beam 111 to form an electrostatic latent image, and after a visible image is formed by toner, the toner image is transferred to a transfer material 105 by a roller 106 to which a voltage of +700 V is applied. Have a process to do.

Further, the photosensitive member charging potential is set such that the dark portion potential is -5.
The voltage was set to 60 V, and the bright portion potential was set to -150 V. 75 g / m ² paper was used as the transfer material.

The toners 1, 3 to 3
A printing durability test was conducted using 7, 9 and 11 under the conditions of a temperature of 23 ° C. and a humidity of 10%.

In the printing durability test, characters were printed at a printing area ratio of about 8% and evaluated as follows.

The contamination of the charging roller with the toner was judged based on the number of durable sheets on which charging unevenness due to contamination of the charging member occurred on the halftone image. The larger the number of sheets up to the occurrence, the better the durability of the toner.

The fog in the early stage of the endurance is determined by fogging the toner adhered to the photoreceptor at the time of developing a solid white image by taping with a Mylar tape, peeling off the toner, and then applying the fogging density on the paper.
The evaluation was made by subtracting the fog density of the tape with only the tape applied. Therefore, the smaller the value, the better the fog suppression.

The transferability in the initial stage of the durability test was determined based on the Macbeth density of the tape-applied toner based on the Macbeth density of the tape-adhered toner remaining on the photoreceptor during solid black image development. The evaluation was performed by subtracting the concentration. Therefore, the smaller the value, the better the transferability.

When no charging unevenness occurred, image printing was continued up to 1500 sheets.

The resolving power in the early stage of durability was evaluated by the reproducibility of one small-diameter isolated dot at 600 dpi, in which the electric field was easily closed by the latent image electric field and it was difficult to reproduce. ◎ Very good: 5 or less defects in 100 ○ Good: 6 to 10 defects in 100 △ Practical: 11 to 19 defects in 100 × Not practical: Defective in 100 Is 20 or more

The anti-offset property was determined by observing the stains generated on the back side of the image sample from the initial stage to the endurance of 100 sheets, and counting the number of sheets generated.

Table 3 shows the obtained results.

[0152]

[Table 3]

[0153]

The polymerized toner of the present invention wherein a monomer composition containing a polymerizable monomer and a specific ester wax composition is suspension-polymerized in an aqueous medium containing a specific carboxylic acid compound as a surfactant. The manufacturing method enables the manufacture of a polymerized toner having excellent performance. That is, the polymerized toner of the present invention obtained by this method contains a specific amount of a specific carboxylic acid compound (including a salt) with respect to the toner and further contains a raw material ester wax in a non-hydrolyzed state. ing. Therefore, a toner having excellent anti-blocking properties and durability and environmental characteristics can be obtained while maintaining good fixing properties. Further, when the production method of the present invention is applied to a color toner, good OHP transparency can be obtained. Furthermore, even when the toner according to the present invention is used in a contact developing method using a cleaner-less toner, it exhibits excellent performance in image characteristics, durability, and offset resistance.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring a charge amount of a toner.

FIG. 2 is a schematic explanatory view of a developing device suitable for the present invention.

FIG. 3 is a schematic view of a one-component image forming apparatus suitable for the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 Suction machine 12 Measuring container 13 500 mesh screen 14 Lid 15 Vacuum gauge 16 Suction port 17 Condenser 18 Electrometer 31 Developing device 32 Developer supply member (roller) 33 Developer regulating member 34 Toner 35 Photoconductor 36 Power supply for developing bias 37 Toner carrier (elastic roller) 100 Developing device 101 Developing blade for coating layer control (made of resin-coated stainless steel) 102 Toner carrier (medium resistance rubber roller) 103 Toner application roller 104 Toner 105 Transfer material 106 Transfer roller 107 Fixing roller Pressure roller 108 Heating roller for fixing 109 Photoconductor 110 Charging roller 111 Laser beam 112 Transfer toner 113 Transfer residual toner 115 Bias power supply for charging roller 116 Bias power supply for transfer roller 117 Bias power supply for toner carrier 118 bias power supply for toner application roller

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Motoki Hisagi, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA01 AA06 AB06 CA04 CA14 CA23 EA07

Claims (9)

[Claims] 1. A polymerized toner obtained by subjecting a monomer composition containing at least a polymerizable monomer and a wax composition to suspension polymerization in an aqueous medium containing a poorly water-soluble inorganic compound and a surfactant to obtain a toner. This is a production method, under the following conditions: The wax composition contains at least an ester wax composed of a carboxylic acid compound having 6 to 40 carbon atoms. At least a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) is used as the surfactant. A method for producing a polymerized toner, characterized by satisfying the following. 2. A carboxylic acid compound (including a salt) constituting at least the ester wax as the surfactant.
The method for producing a polymerized toner according to claim 1, wherein: 3. The method according to claim 1, wherein the alcohol compound constituting the ester wax is a monoalcohol, and / or the carboxylic acid compound constituting the ester wax is a monocarboxylic acid. A method for producing a polymerized toner. 4. A composition comprising at least a binder resin, a colorant and a wax composition, wherein the wax composition comprises at least an ester wax, and the ester wax is a carboxylic acid having 6 to 40 carbon atoms. Consists of compounds. The polymerized toner contains a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) in an amount of 30 to 3000 based on the mass of the toner.
ppm. A polymerized toner characterized by satisfying the following. 5. The polymerized toner according to claim 4, wherein the carboxylic acid compound contained in the toner is a carboxylic acid compound constituting the ester wax. 6. The method according to claim 4, wherein the alcohol compound constituting the ester wax is a monoalcohol, and / or the carboxylic acid compound constituting the ester wax is a monocarboxylic acid. Polymerized toner. 7. A polymerization obtained by subjecting a monomer composition containing at least a polymerizable monomer, a colorant and a wax composition to suspension polymerization in an aqueous medium containing a poorly water-soluble inorganic compound and a surfactant. The wax composition contains at least an ester wax composed of a carboxylic acid compound having 6 to 40 carbon atoms. 30 to 3000 ppm of a carboxylic acid compound (including a salt) having at least 6 to 40 carbon atoms based on the mass of the toner
contains. It is manufactured using at least a carboxylic acid compound having 6 to 40 carbon atoms (including a salt) as the surfactant. A polymerized toner satisfying the following. 8. A carboxylic acid compound contained in a toner and a carboxylic acid compound used as a surfactant,
The polymerized toner according to claim 7, which is a carboxylic acid compound constituting the ester wax. 9. The polymerization according to claim 7, wherein the alcohol compound constituting the ester wax is a monoalcohol and / or the carboxylic acid compound constituting the ester wax is a monocarboxylic acid. toner.