JPH09190012A - Electrostatic charge image developing toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form dignified images having improved fixability and suppress glass of images by specifying the crosslinking degree of primary particles to a specific range with the insoluble component of tetrahydrofuran. SOLUTION: The crosslinking degree of the primary particles of the electrostatic charge image developing toners consisting of coloring particles formed by flocculating and fusing the primary particles of a polymer is specified to 0.01wt.% in the insoluble component of the tetrahydrofura. The toners are formed by associating and fusing plural pieces of the polymer particles having a grain size below the desired toner grain size. The polymer particles are produced by using a known polymn. method. For example, an emulsion polymn. method, suspension polymn. method, soap-free polymn. method, seed polymn. method, molecule dispersion method, two-stage swelling, etc., are used. The method of obtaining the polymer particle dispersion liquid of submicron by using the emulsion polymn. method and associating and fusing plural pieces of such dispersion particles is more preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in an image forming apparatus used in a copying machine, a printer or the like, and an image forming method using the toner.

[0002]

2. Description of the Related Art In recent years, electrostatic image development represented by an electrophotographic developing system has been used in various fields. For example, it is used not only in copying machines but also in the fields of printers, which are output terminals of computers, color copying machines, color printers, and the like, and as the usage in these fields progresses, the demand for image quality is increasing.

For this reason, the demand for the toner itself has increased, and in addition to image quality performance which has been conventionally regarded as a problem such as resolution, various requirements such as improvement in fixing fastness and texture of a finished image have been made. .

However, in these points, there are still many unexamined parts, and the superiority or inferiority may change depending on the preference and use of each individual, and it is not established technically at present.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of forming a solid image with improved fixability and reduced image gloss.

[0006]

The object of the present invention is attained by adopting one of the following constitutions.

(1) In an electrostatic charge image developing toner comprising colored particles formed by aggregating and fusing polymer primary particles,
A toner for developing an electrostatic charge image, wherein the degree of crosslinking of the primary particles is 0.01% by weight to 50% by weight in tetrahydrofuran insoluble matter.

(2) In an electrostatic charge image developing toner comprising colored particles obtained by aggregating and fusing polymer primary particles,
The BET specific surface area of the colored particles is 5 m ² / g or more, and the toner for developing an electrostatic image as described in (1) above.

(3) In an electrostatic charge image developing toner comprising colored particles obtained by aggregating and fusing polymer primary particles,
The toner for developing an electrostatic charge image according to (1) or (2), wherein the colored particles have a shape factor of 1.01 to 1.5.

(4) In an image forming method for developing an electrostatic latent image on a photoconductor with a toner image, the toner comprises electrostatically charged image development comprising colored particles formed by aggregating and fusing polymer primary particles. An image forming method, wherein the primary particles have a crosslinking degree of 0.01 to 50% by weight in tetrahydrofuran-insoluble matter, which is an electrostatic image developing toner.

(5) In an image forming method for developing an electrostatic latent image on a photoconductor with a toner image, the toner comprises electrostatically charged image development comprising colored particles formed by aggregating and fusing polymer primary particles. (4) The image forming method according to (4), wherein the colored particle has a BET specific surface area of 5 m ² / g or more.

(6) In an image forming method for developing an electrostatic latent image on a photoconductor with a toner image, the toner comprises electrostatically charged image development comprising colored particles formed by aggregating and fusing polymer primary particles. Toner having a shape factor of 1.0
The image forming method according to (4) or (5), which is 1 to 1.5.

(7) In an image forming method for transferring a toner image formed on an image support onto a transfer material, the toner comprises colored particles formed by aggregating and fusing polymer primary particles. An image forming method, which is a toner for developing a charge image, wherein the degree of crosslinking of the primary particles is 0.01 to 50% by weight in tetrahydrofuran-insoluble matter.

(8) In an image forming method for transferring a toner image formed on an image support onto a transfer material, the toner comprises colored particles formed by aggregating and fusing polymer primary particles. A toner for developing a charge image, comprising B of the colored particles
The image forming method according to (7), which is a toner for developing an electrostatic charge image having an ET specific surface area of 5 m ² / g or more.

(9) In an image forming method for transferring a toner image formed on an image support onto a transfer material, the toner comprises colored particles formed by aggregating and fusing polymer primary particles. A toner for developing a charge image, wherein the color particles have a shape factor of 1.01 to 1.5 (7)
Alternatively, the image forming method described in (8).

(10) In an image forming method, in which a toner image formed on an image support is transferred onto a transfer material and then the toner remaining on the support is cleaned, the toner is a polymer primary particle. A toner for developing an electrostatic charge image, which comprises colored particles obtained by aggregating and fusing, wherein the degree of crosslinking of the color particles is 0.01% by weight to 50% by weight in tetrahydrofuran-insoluble matter. An image forming method characterized by being a toner.

(11) In the image forming method, in which the toner image formed on the image support is transferred onto a transfer material and then the toner remaining on the support is cleaned, the toner is a polymer primary particle. A toner for developing an electrostatic charge image comprising colored particles obtained by aggregating and fusing
The image forming method according to (10), which is an electrostatic charge image developing toner having an ET specific surface area of 5 m ² / g or more.

(12) In an image forming method, in which a toner image formed on an image support is transferred onto a transfer material and then the toner remaining on the support is cleaned, the toner is a polymer primary particle. A toner for developing an electrostatic charge image comprising colored particles formed by aggregating and fusing, wherein the shape factor of the color particles is 1.01 to 1.5. The image forming method according to (10) or (11).

Toner Production Method The toner of the present invention is produced by associating and fusing a plurality of polymer primary particles having a particle diameter not larger than a desired toner particle diameter. The polymer particles are produced by using a known polymerization method. For example, emulsion polymerization method, suspension polymerization method, dispersion polymerization method, soap-free polymerization method, seed polymerization method, molecular diffusion method, two-step swelling method, etc. are used. Preferred is a method of obtaining a submicron polymer particle dispersion using an emulsion polymerization method, and associating and fusing a plurality of the dispersed particles.

To make a toner further, an aggregating agent is added to the above-mentioned polymer primary particle dispersion liquid, an organic solvent which is infinitely soluble in water is further added, and the mixture is heated at a temperature higher than the glass transition temperature of the polymer primary particles. It can be manufactured by fusing particles. The internal additive essential as a toner and the internal additive added as required include a colorant, a fixing property improving agent, a charge control agent, and the like, which are added during the polymerization of the polymer primary particle dispersion or at the time of association. It is sometimes added in the form of an aqueous dispersion. In this case, it is particularly preferably added during the polymerization. As a result, the internal additive is uniformly compounded with the polymer particles, and when the toner is used, the internal additive is also uniformly present in the toner particles, and stable toner characteristics can be obtained.

Since the primary particles used in the present invention are cross-linked, they generally do not easily exhibit a glass transition temperature. Therefore, heat fusion is difficult to proceed. Therefore, it is necessary to raise the reaction temperature in order to adjust the shape of the toner particles sufficiently. Generally 90 ℃ ~ 1
It is performed in the range of 80 ° C. At this temperature, since the boiling point of the reaction liquid is exceeded, it is preferable to use a pressure type reactor.

Copolymerization ratio of cross-linking monomer The cross-linking monomer varies in degree of cross-linking depending on the reactivity of the monomer itself, polymerization conditions, etc., but tetrahydrofuran (THF)
In order to set the insoluble content of 0.01 to 50% by weight,
The copolymerization ratio is preferably in the range of 0.01% by weight to 5% by weight. When the THF insoluble content is less than this range, the fixing property and the non-glossiness of the image are not significantly affected.
On the other hand, if it exceeds this range, the fixing property becomes extremely poor.

Here, tetrahydrofuran (TH
The insoluble matter of F) was measured by adding the polymer to THF at 25 ° C. so as to have a concentration of 1% by weight, stirring the mixture for 24 hours, and then filtering, and calculating from the weight of the solid content remaining. It

Crosslinking Monomer As the crosslinking monomer, an ethylenic polyfunctional monomer having radical polymerizability is used. As an example, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate,
Examples include neopentyl glycol diacrylate. It is also possible to use a monomer having a reactive group in the pendant group, such as glycidyl methacrylate, methylol acrylamide, or acrolein. Radical-polymerizable ethylenically unsaturated polyfunctional monomers are preferred, and divinylbenzene is more preferred.

One of the desirable modes of the toner of the present invention is
The BET value specific surface area of the colored particles is 5 m ² / g or more, but this BET value specific surface area is measured by the one-point method of nitrogen adsorption method. Specifically, Shimadzu Flowsorb 2 is used.
Measured with 300 measuring devices.

One of the desirable modes of the toner of the present invention is that the colored particles have a shape factor of 1.01 to 1.5. This shape factor is defined by the perimeter of the particle / circumference of the circle of the particle, and is specifically defined by the following formula.

[0027]

[Equation 1]

In the above formula, L represents the perimeter of the particle (μm), and A represents the projected area of the particle (μm ² ).

L and A in the above formula project a particle and measure L and A at the time of projection. Specifically, L and A are projected, and each L and A is n = 100 to 1000. The average value of is measured with an image analyzer.

A toner which can achieve the object of the present invention better is a toner made of colored particles having the above-mentioned characteristics, which is a toner having a relatively spherical shape and a large surface area, and having a specific shape. Since it has a large surface area, it is presumed that the above-mentioned various objects of the present invention can be achieved.

Materials and modes used for carrying out the present invention will be further described.

Monomer constituting the toner resin
Specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethyl. Styrene, 2,4-dimethylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene. Such as styrene or styrene derivatives, aromatic vinyl compounds such as vinylnaphthalene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate. , 2-ethylhexyl methacrylate, methacrylate Lil, lauryl methacrylate,
Methacrylic acid ester derivatives such as phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, acrylic Such as acrylic acid ester derivatives such as n-octyl acid salt, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc.
-Methylene aliphatic monocarboxylic acid esters; olefins such as ethylene, propylene and isobutylene; vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride,
Vinyl halides such as vinylidene fluoride; vinyl esters such as vinyl propionate, vinyl acetate, vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. Vinyl ketones; N-vinylcarbazole, N-vinylindole,
There are N-vinyl compounds such as N-vinylpyrrolidone and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. Among these monomers, aromatic vinyl compounds and α-methylene aliphatic monocarboxylic acid esters are preferable.

These vinyl-based monomers can be used alone or in combination to obtain a copolymer, which can be used in a toner. Further, as the monomer constituting the resin, those having an ionic dissociative group can be used in combination. For example, those having a substituent such as a carboxy group, a sulfo group, and a phospho group as a constituent group of a monomer, specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, Maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate Etc.

In the present invention, since the resin obtained as described above is obtained in the form of fine particles, particularly when it is obtained by the emulsion polymerization method, a flocculating agent is used and a solvent infinitely soluble in water is further added. Then, by heat-treating at a temperature not lower than the glass transition point of the obtained resin, particles (toner) having a desired particle diameter can be obtained.

When producing the toner of the present invention, the aggregating agent used is not particularly limited,
Those selected from metal salts are preferably used. Specifically, as the monovalent metal, for example, sodium, potassium,
Alkali metal salts such as lithium, divalent metals such as alkaline earth metal salts such as calcium and magnesium, divalent metal salts such as manganese and copper, and trivalent metal salts such as iron and aluminum. And specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, inexpensive zinc, copper sulfate, magnesium sulfate,
Examples thereof include manganese sulfate and the like. These may be used in combination.

These coagulants are used by adding them at a critical coagulation concentration or more. The critical aggregation concentration is an index relating to the stability of the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical coagulation concentration greatly changes depending on the emulsified component and the dispersant itself. For example, Seizo Okamura et al., “Polymer Chemistry Vol.
17, p601 (1960) edited by The Society of Polymer Science, Japan, etc., and a detailed critical aggregation concentration can be obtained. Further, as another method, a desired salt is added to the target particle dispersion at a different concentration, and the resulting dispersion is subjected to ζ (zeta).
The potential can be measured, and the salt concentration at which this value changes can be determined as the critical aggregation concentration.

The coagulant used in the present invention may be added in an amount not less than the critical coagulation concentration, preferably not less than 1.2 times the critical coagulation concentration, and more preferably not less than 1.5 times the critical coagulation concentration. .

The solvent which is infinitely soluble in water to be used is a colored polymer dispersion, that is, a solvent which is infinitely soluble in an aqueous dispersion, and this solvent is a resin formed in the present invention. Those that do not dissolve are selected. Specific examples include alcohols such as methanol, ethanol, propanol, isopropanol, t-butanol, methoxyethanol and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. Particularly, ethanol, propanol and isopropanol are preferable.

The amount of the solvent that dissolves infinitely is 1 to 300% by volume with respect to the polymer-containing dispersion liquid to which the coagulant is added.
Is preferred.

Various methods can be used as the polymerization method for forming the resin used in the toner of the present invention.
The above-mentioned emulsion polymerization method is particularly preferable.

Various colorants and property improvers such as fixability improvers can be used in the toner of the present invention. Carbon black, magnetic materials, dyes, pigments and the like can be arbitrarily used as the colorant that can be used, and channel black, furnace black, acetylene black, thermal black / lamp black and the like can be used as carbon black. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used. As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5,
48: 1, 53: 1, 57: 1, 122, 1
39, 144, 149, 166, 177, 1
78, 222, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, Same 17 and Same 9
3, 94, 138, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. These colorants have a number average primary particle diameter of about 10 to 200.
It is preferable to use particles having a size of about nm dispersed in the toner.

As a method for adding the colorant, when the toner of the present invention is prepared by an emulsion polymerization method, the polymer itself is prepared by an emulsion polymerization method and then added at the stage of aggregating by adding an aggregating agent. A method or a method of adding a colorant at the stage of polymerizing the monomer can be used. In addition,
When the colorant is added at the stage of preparing the polymer, it is preferable to treat the surface with a coupling agent or the like before use so as not to hinder the radical polymerizability.

Further, low molecular weight polypropylene (number average molecular weight = 1,500 to 9.00) as a fixing property improving agent.
0) or low molecular weight polyethylene may be added. Further, an azo-based metal complex, a quaternary ammonium salt, or the like may be used as a charge control agent. These property modifiers are usually added to the toner in the same manner as the colorants.

From the viewpoint of imparting fluidity, it may be added to colored particles obtained by polymerizing inorganic fine particles and organic fine particles. In this case, it is preferable to use inorganic fine particles, and it is preferable to use inorganic oxide particles such as silica, titania, and alumina, and further, these inorganic fine particles are subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, or the like. Is preferred.

The toner of the present invention can be produced by associating a plurality of the above-mentioned polymers themselves. In this case, the metal as the aggregating agent is stirred with respect to the dispersion liquid of the polymer particles. It can be obtained by adding a salt in an amount not less than the critical coagulation concentration, further adding the above-mentioned solvent infinitely soluble in water, and further heat-treating at a temperature not lower than the glass transition temperature of the polymer.

The toner of the present invention has a BET value specific surface area of 5 m.
² / g or more is desirable, and from a technical point of view it is 150 m ² / g or less, preferably 100 m ² / g
Or less, and particularly preferably 5 to 50 m ² / g.

The toner of the colored particles of the present invention preferably has a shape factor of 1.01 to 1.5, more preferably 1.05 to 1.3.

The method for producing the toner of the present invention is not particularly limited as described above, but preferably, JP-A-5-265252, JP-A-6-329947 and JP-A-6-223953 are used. The method described in the application is used. That is, a method of associating a plurality of fine particles composed of a resin, a colorant and the like, particularly a method of treating them in water with an aggregating agent having a concentration equal to or higher than the critical aggregation concentration and an organic solvent infinitely soluble in water is preferable. It is used.
Further, the toner having the BET value specific surface area and shape factor of the present invention can be formed by heat fusion at the glass transition temperature or higher of the formed polymer itself.

The particle diameter of the toner of the present invention itself is arbitrary, but a toner having a small particle diameter is more likely to exert the effect of the present invention and exhibits a great improvement effect, and its volume average particle diameter is 2 to 10 μm.
Those having 3 to 9 μm are particularly preferable.
This particle size can be controlled by the concentration of the flocculant, the amount of the organic solvent added, and the composition of the polymer itself.

The toner of the present invention is used as a one-component magnetic toner containing a magnetic material, used as a two-component developer mixed with a so-called carrier, or used as a non-magnetic toner alone. However, in the present invention, it is particularly preferable to use it as a two-component developer which is used as a mixture with a carrier.

As the carrier constituting the two-component developer, either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin coated carrier in which the magnetic material particle surfaces are coated with a resin or the like is used. Good. The average particle size of this carrier is 30 to 1 in terms of volume average particle size.
50 μm is preferred. The resin for coating is not particularly limited, but examples thereof include styrene-acrylic acid ester resin and silicone resin.

The developing system in which the toner of the present invention can be used is not particularly limited, and it can be suitably used in a contact developing system or a non-contact developing system. For contact type development, the layer thickness of the developer having the toner of the present invention is 0.1 to 8 mm, preferably 0.4 to 5 m in the developing area.
m, so that the developer is erected in the developing area, which is a so-called magnetic brush developing method. In this case, the gap between the photoconductor and the developer carrying member is preferably 0.15 to 7 mm, particularly 0.2 to 4 mm.

In the non-contact type developing system, the developer layer formed on the developer carrying member does not come into contact with the photoconductor, and the developer layer is a thin layer in order to constitute this developing system. Is preferably formed. In this method, a developer layer having a thickness of 20 to 500 μm is formed in a development region on the surface of the developer carrier, and a gap between the photoconductor and the developer carrier has a larger gap than the developer layer.

In the non-contact developing method, the thin layer is formed by a method of pressing a developer layer regulating rod against the surface of a developer carrying member or a magnetic blade using magnetic force. Further, there is also a method of contacting a surface of a developer bearing member with a urethane blade, a phosphor bronze plate or the like to regulate the developer layer. The pressing force of the pressing regulating member is preferably from 1 to 15 gf / mm. When the pressing force is small, the conveyance is likely to be unstable because the regulating force is insufficient. On the other hand, when the pressing force is large, the stress on the developer is increased, and the durability of the developer is likely to be reduced. A preferred range is 3 to 10 gf / mm. Further, in the non-contact developing method, it is preferable to apply a developing bias voltage at the time of development, but in this case, a method of applying only a DC component or a method of applying an AC bias in a superimposed manner may be used.

The size of the developer carrying member is 10 in diameter.
It is preferable that the magnet is held within a range of -40 mm.
If the diameter is too small, the mixing of the developer will be insufficient, and it will be difficult to ensure sufficient mixing to give sufficient charge to the toner.If the diameter is too large, the centrifugal force against the developer will be insufficient. It becomes large and the problem of toner scattering tends to occur.

An example of the non-contact developing system will be described below with reference to FIG.

FIG. 1 is a schematic view of a non-contact developing type developing section that can be suitably used in the image forming method of the present invention. 1 is a photoconductor, 2 is a developer carrier, and 3 is the toner of the present invention. The contained two-component developer, 4 is a developer layer regulating member, 5 is a developing region, 6 is a developer layer, and 7 is a power source for forming an alternating electric field.

The two-component developer containing the toner of the present invention is carried by the magnetic force on the developer carrying member 2 having the magnet 2B therein, and is carried to the developing area 5 by the movement of the developing sleeve 2A. At the time of this conveyance, the developer layer 6 is regulated by the developer layer regulating member 4 in the developing region 5 to a layer of that thickness so as not to come into contact with the photoreceptor 1.

The minimum gap (Dsd) of the developing area 5 is the thickness of the developer layer 6 conveyed to that area (preferably 20 to 5).
00 μm), for example, about 100 to 1000 μm. The power source 7 for forming the alternating electric field is preferably an alternating current having a frequency of 1 to 10 kHz and a voltage of 1 to 3 kVp-p. The power supply 7 may have a configuration in which direct current is added to alternating current in series. When applying a DC voltage, 300 to 800 V is preferable.

When the toner of the present invention is applied to a color image forming system, a system in which a monochromatic image is formed on a photoconductor and sequentially transferred to an image support (this system is referred to as a sequential transfer system and is shown in FIG. 2). Alternatively, a method of developing a single color image on a photoconductor a plurality of times to form a color image and then collectively transferring the image to an image support (this is referred to as a batch transfer method and is shown in FIG. 3).
And the like.

In the specification of the present invention, the latent image is formed and toner-developed on the photoconductor. However, the latent image is not particularly limited to the photoconductor and has the above-mentioned functions. It may be on the electrostatic latent image support.

The image forming method shown in FIGS. 2 and 3 will be described in detail below.

As the developer carrying member used in the present invention, as shown in FIGS. 1, 2 and 3, a developing device in which a magnet 2B is incorporated inside the carrying member is used to form the surface of the developer carrying member. As the sleeve 2A to be used, aluminum, stainless steel whose surface is oxidized, or stainless steel is used.

An example of the sequential transfer method shown in FIG. 2 will be described below.

Reference numeral 11 is a charging device which is a charging electrode, and 12 is a developing unit which is a developing device for loading yellow, magenta, cyan and black toners, respectively, and is divided into four containers corresponding to four color toners. . The basic configuration of these developing units is the same as the schematic diagram of the developing unit shown in FIG. 14 is a photoconductor drum, 13 is a cleaning unit, 15 is a holding unit for temporarily holding a monochromatic color toner image formed on the photoconductor drum, and further is for holding the next monochromatic toner image thereon.
A transfer drum that finally forms the desired multicolor image.
Reference numeral 16 is a transport unit for transporting a transfer material on which a toner image on the transfer drum is transferred, 17 is an inside of the transfer drum 15, and an attracting electrode for corona-discharging from inside to electrostatically attract the transfer material to the drum. 18 is a transfer electrode for sequentially transferring the toner image formed on the photoconductor drum 14 to the transfer drum, 19 is a peeling electrode for peeling the transfer material electrostatically adsorbed on the transfer drum 15, and 20 is after peeling the transfer material. , A removal electrode for removing charges remaining on the transfer drum.

By the charger 11 on the photosensitive drum 14,
A uniform charge is formed, followed by imagewise exposure (means not shown) to form an electrostatic latent image. This electrostatic latent image is developed by a developing device that holds one color toner (for example, black toner) of the developing unit 12, and a one color toner image is formed on the photosensitive drum 14. On the other hand, the transfer material transported by the transport unit 16 onto the transfer drum 15 is attracted to the adsorption electrode 17.
Is electrostatically adsorbed on the transfer drum and is conveyed to the transfer section.

At the transfer portion, the toner image formed on the photosensitive drum 14 is transferred onto the transferred transfer material. The toner remains on the photosensitive drum 14 after the transfer of the transfer image, and the remaining toner is cleaned by the cleaning unit 13 and used for the next process. When forming a multicolor image, toner images of other colors are formed by development according to a similar process and transferred one by one to the transfer drum 15. Eventually, a desired toner image is formed on the transfer material adsorbed on the transfer drum 15. The transfer material on which a desired toner image is formed is peeled off by the peeling electrode 19 and is conveyed to the fixing section to obtain the final fixed multicolor toner image. On the other hand, the transfer drum 15 has the remaining charges removed by the removing electrode 20, and is used in the next process.

Next, the batch transfer method will be described with reference to FIG.

Since each part of the apparatus is the same as the example of FIG. Here, reference numeral 21 denotes a transport unit that transfers the toner image while transporting the transported transfer material. Photoconductor drum 1
Electric charges are uniformly formed on the surface 4 by a charging electrode, and then an electrostatic latent image is formed by a latent image forming means (means not shown).
This electrostatic latent image is developed by a developing device having a toner (for example, black toner) of one color of the developing unit 12, and a toner image of one color is formed on the photosensitive drum. In the illustrated example, this toner image is not transferred, and the charge electrode 11 uniformly forms an electric charge again on the photosensitive drum having the toner image as it is, and further an electrostatic latent image is formed. Then, it is developed by a developing device having a toner of a color different from the above, and a toner image of another color is formed by being superposed on the previous toner image. During this time, cleaning unit 1
3, the transfer electrode 18, and the transport unit 21 do not operate, and are retracted from the photoconductor drum 14 so as not to disturb the toner image on the photoconductor drum 14.

After the desired image formation is completed and a multicolor toner image is formed, the toner image on the photosensitive drum is transferred onto the transfer material carried by the carrying unit 16 while being carried by the carrying section 21. The toner image is transferred by the electrode 18. The transfer material carrying the transferred toner image is transported to a fixing unit, where it is fixed, and a final multicolor toner image is formed on the transfer material. After the toner image is transferred, the toner remains on the photosensitive drum 14, so that the cleaning unit 13 cleans the toner and the toner is used in the next process.

The toner image formed on the photosensitive member by the various methods described above is transferred to a transfer material such as paper in a transfer process. The transfer method is not particularly limited, and various methods such as a so-called corona transfer method and a roller transfer method can be adopted.

Since the toner of the present invention has a high transfer efficiency and a small amount of toner remains on the photosensitive member, when the blade cleaning method is used, for example, the pressing force of the blade to the photosensitive member can be reduced, and the toner of the photosensitive member can be reduced. It also has an effect that it can contribute to a longer life.

After the toner image is transferred to the transfer material, the toner remaining on the photoconductor is removed by cleaning, and the photoconductor is repeatedly used in the next process.

The mechanism for cleaning in the present invention is not particularly limited, and a known cleaning mechanism such as a blade cleaning method, a magnetic brush cleaning method, a fur brush cleaning method can be arbitrarily used. A preferable cleaning mechanism is a blade cleaning method using a so-called cleaning blade for the above-described reason.

[0075]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

(Colored Particles) Colored Particle Production Example 1 Carbon black (Regal 330R: manufactured by Cabot Corporation) was used as an aluminum coupling agent (Planeact AL).
-M: manufactured by Ajinomoto Co., Inc., 10.67 g was added to an aqueous solution prepared by dissolving 4.92 g of sodium dodecylsulfate in 120 ml of pure water, and ultrasonic waves were radiated while recognizing each of them, and an aqueous dispersion of carbon black was obtained. Was adjusted. Also, low molecular weight polypropylene (number average molecular weight = 3200) was emulsified in water with a surfactant while heating, and the solid content concentration = 20.
A weight% emulsion dispersion was prepared. 43 g of a low molecular weight polypropylene emulsion dispersion was mixed with the above carbon black dispersion, and 90.0 g of styrene monomer, 10.9 g of divinylbenzene (active ingredient = 55%), 18.0 g of n-butyl acrylate, and 6. Methacrylic acid monomer. 0g, te
rt-dodecyl mercaptan 3.3g, degassed pure water 85
After adding 0 ml, while stirring under a nitrogen stream,
The temperature was raised to ° C. Then, 200 ml of pure water in which 6.1 g of potassium persulfate was dissolved was added, polymerization was carried out at 70 ° C. for 6 hours, and then cooled to room temperature. The obtained carbon black-containing colored particle dispersion was designated as "dispersion 1". The particle size of this dispersion is the light scattering electrophoresis particle size measuring device ELS-8.
00 (Otsuka Electronics Co., Ltd.), and the tetrahydrofuran-insoluble matter was measured by using a polymer obtained by removing the colorant and low molecular weight polypropylene from the above polymerization.

600 ml of this "dispersion liquid 1" was added to the pressure reactor.
To 160 mol of a 2.7 mol / l potassium chloride aqueous solution.
94 ml of isopropyl alcohol, 5.4 g of polyoxyethylene octyl phenyl ether (average degree of polymerization of ethylene oxide is 10), and 40 ml of pure water.
An aqueous solution dissolved in was added.

After further applying a pressure of 5 kg / cm ² , the internal temperature was raised to 130 ° C. and the reaction was carried out for 6 hours, followed by cooling to room temperature, releasing the pressure, filtering the reaction solution, washing with water and drying. Then, the colored particles of the present invention were obtained. This is "colored particle 1"
And

Colored Particle Production Example 2 The amount of the monomer added in the above colored particle production example 1 was 93.0 g of styrene monomer, 5.45 g of divinylbenzene (active ingredient = 55%), and 1 of n-butyl acrylate.
Colored particles of the present invention were obtained in the same manner except that 8.0 g and 6.0 g of methacrylic acid monomer were used. The dispersion obtained here is referred to as "dispersion 2", and the colored particles are referred to as "colored particles 2".
And

Colored Particle Production Example 3 The amount of the monomer added in Colored Particle Production Example 1 was 94.8 g of styrene monomer, 2.18 g of divinylbenzene (active ingredient = 55%), and 1 of n-butyl acrylate.
Colored particles of the present invention were obtained in the same manner except that 8.0 g and 6.0 g of methacrylic acid monomer were used. The dispersion obtained here is referred to as "dispersion 3", and the colored particles are referred to as "colored particles 3".
And

Colored Particle Production Example 4 The amounts of the monomers added in the above colored particle production example 1 were 91.08 g of styrene monomer, 0.22 g of divinylbenzene (active ingredient = 55%), 18.0 g of n-butyl acrylate and methacrylic acid. Colored particles of the present invention were obtained in the same manner except that the amount of the monomer was changed to 6.0 g. The dispersion obtained here was designated as "dispersion 4", and the colored particles were designated as "colored particles 4".

Colored Particle Production Example 5 The amount of the monomer added in the above colored particle production example 1 was 95.98 g of styrene monomer, 0.02 g of divinylbenzene (active ingredient = 55%), 18.0 g of n-butyl acrylate, and methacrylic acid. Colored particles of the present invention were obtained in the same manner except that the amount of the monomer was changed to 6.0 g. The dispersion obtained here was designated as "dispersion 5", and the colored particles were designated as "colored particles 5".

Colored Particle Production Example 6 Instead of the surface-treated carbon black in the above colored particle production example 3, C.I. I. Pigment Yell
Colored particles of the present invention were obtained in the same manner except that ow 17 was used. The dispersion obtained here was designated as "dispersion 6", and the colored particles were designated as "colored particles 6".

Colored Particle Production Example 7 Instead of the surface-treated carbon black in the above colored particle production example 3, C.I. I. Pigment Red
Colored particles of the present invention were obtained in the same manner except that 122 was used. The dispersion obtained here was designated as "dispersion 7", and the colored particles were designated as "colored particles 7".

Colored Particle Production Example 8 In place of the carbon black surface-treated in Colored Particle Production Example 3 above, C.I. I. Pigment Blue
The colored particles of the present invention were obtained in the same manner except that 15: 3 was used. The dispersion liquid obtained here was designated as "dispersion liquid 8", and the colored particles were designated as "colored particles 8".

Comparative colored particle production example 1 The amount of the monomer added in the above colored particle production example 1 was 89.78 g of styrene monomer, 13.32 g of divinylbenzene (active ingredient = 55%), 18.4 g of n-butyl acrylate, Colored particles of the present invention were obtained in the same manner except that 6.1 g of methacrylic acid monomer was used. The colored particles obtained here were designated as "Comparative colored particles 1".

Comparative colored particle production example 2 The same as the above except that the amount of the monomer added in the colored particle production example 1 was changed to 98.1 g of styrene monomer, 18.4 g of n-butyl acrylate and 6.1 g of methacrylic acid monomer. The colored particles of the present invention were obtained. The colored particles obtained here were designated as "Comparative colored particles 2".

The average particle size and THF insoluble content of the obtained colored particles, dispersions 1 to 8 of comparative colored particles, and comparative dispersions 1 to 2 are shown in Table 1 below.

[0089]

[Table 1]

Colored Particles 1-8 and Comparative Colored Particles 1-2
For, the volume average particle size and particle size distribution were measured by using a laser diffraction particle size analyzer SALD-1100: manufactured by Shimadzu Corporation, and the BET specific surface area was measured using Flowsorb 2300: manufactured by Shimadzu Corporation using a nitrogen adsorption one-point method. did. Further, the particle shape is shown in Table 2 by using a high-speed image analyzer SPICCA: manufactured by Nippon Avionics Co., Ltd., and using the shape factor defined by the perimeter of the toner particle / the circumference of the particle equivalent circle.

[0091]

[Table 2]

(Preparation of Toner) Colored Particles 1 to 8
Further, 1 wt% of hydrophobic silica (temporary particle diameter = 12 nm) was added to each of Comparative colored particles 1 to Comparative colored particle 2 to obtain a toner. These are designated as "toner 1" to "toner 8" and "comparative toner 1" to "comparative toner 2".

(Preparation of Developer) Further, the above toner was mixed with a ferrite carrier having a volume average particle size of 50 μm coated with a styrene-acrylic acid ester resin, and the above “toner 1” to “toner 8” and “comparative toner” were mixed. “Developer 1” to “Developer 8” and “Comparative Developer 1” to “Comparative Developer 2” corresponding to 1 ”to“ Comparative Toner 2 ”.

(Evaluation Method) The evaluation of the developer is performed by the copying machine Kon.
ica U-BIX3135 (manufactured by Konica Corporation) was used.

Fixability Test Absolute reflection density of 1.
Development was carried out to 0, and a rubbing test was carried out as a fixing property test after fixing, and the fixing ratio was calculated from the difference in reflection density.

Image Evaluation A test chart was copied using each developer, and sensory evaluation of the image was performed.

The evaluation was carried out on the following four scales: ⊚: very good, ∘: good, Δ: poor, ×: very poor, with respect to the texture and weight of the image.

The results are shown below.

[0099]

[Table 3]

The developers 1 to 8 in the present invention are the fixing test,
It is understood that the performances of image evaluation are at a level where there is no problem in practical use, whereas the comparative developers 1 and 2 other than the present invention cannot obtain sufficient characteristics in both characteristics.

In the comparative developer 2, offset occurred.

[0102]

According to the present invention, it is possible to provide a method for forming a solid image with improved fixability and suppressed image gloss.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a non-contact developing system.

FIG. 2 is a schematic diagram showing an example of a sequential transfer system.

FIG. 3 is a schematic view showing an example of a batch transfer method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Developer carrier 2A Development sleeve 2B Magnet 3 Two-component developer (contains toner of the present invention) 4 Developer layer regulating member 5 Development area 6 Developer layer 7 Power supply 11 for forming alternating electric field 11 Charger 12 Development Unit 13 Cleaning Unit 14 Photoreceptor Drum 15 Transfer Drum 16 Conveying Unit 17 Adsorption Electrode 18 Transfer Electrode 19 Peeling Electrode 20 Eliminating Electrode 21 Conveying Section

Continuation of the front page (72) Inventor Chie Kikuchi 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (12)

[Claims] 1. A toner for developing an electrostatic charge image comprising colored particles obtained by aggregating and fusing polymer primary particles, wherein the degree of crosslinking of the primary particles is 0.01 in tetrahydrofuran.
A toner for developing an electrostatic charge image, characterized in that the content is from 50% by weight to 50% by weight. 2. A toner for developing an electrostatic charge image comprising colored particles obtained by aggregating and fusing polymer primary particles, wherein the BET specific surface area of the colored particles is 5 m ² / g or more. Item 1. The toner for developing an electrostatic charge image according to Item 1. 3. A toner for developing an electrostatic charge image, comprising colored particles obtained by aggregating and fusing polymer primary particles, wherein the shape factor of the colored particles is 1.01 to 1.5. The toner for developing an electrostatic image according to claim 1 or 2. 4. An electrostatic charge image developing method for forming an electrostatic latent image on a photoreceptor with a toner image, the toner comprising colored particles formed by aggregating and fusing polymer primary particles. An image forming method, wherein the toner is a toner for developing an electrostatic charge image, wherein the degree of crosslinking of the primary particles is 0.01% by weight to 50% by weight in tetrahydrofuran-insoluble matter. 5. An electrostatic charge image developing method for developing an electrostatic latent image on a photoreceptor with a toner image, the toner comprising colored particles formed by aggregating and fusing polymer primary particles. A toner having a BET specific surface area of 5 m ²
5. The image forming method according to claim 4, wherein the toner is an electrostatic image developing toner having a toner content of at least 1 / g. 6. An image forming method for developing an electrostatic latent image on a photoconductor with a toner image, wherein the toner comprises colored particles formed by aggregating and fusing polymer primary particles. The toner has a shape factor of 1.01 to 1
6. The image forming method according to claim 4, wherein the image forming ratio is 1.5. 7. An image forming method for transferring a toner image formed on an image support onto a transfer material, wherein the toner comprises colored particles formed by aggregating and fusing polymer primary particles. An image developing toner, wherein the degree of crosslinking of the primary particles is 0.01% by weight to 5% by weight in tetrahydrofuran-insoluble matter.
An image forming method, wherein the toner is 0% by weight of an electrostatic image developing toner. 8. An image forming method for transferring a toner image formed on an image support onto a transfer material, wherein the toner comprises colored particles formed by aggregating and fusing polymer primary particles. The image forming method according to claim 7, which is an image developing toner, wherein the BET specific surface area of the colored particles is 5 m ² / g or more. 9. An image forming method for transferring a toner image formed on an image support onto a transfer material, wherein the toner comprises colored particles formed by aggregating and fusing polymer primary particles. 9. The image forming method according to claim 7, wherein the image forming toner is a toner having a shape factor of 1.01 to 1.5. 10. In an image forming method, comprising: transferring a toner image formed on an image support to a transfer material, and then cleaning the toner remaining on the support, wherein the toner comprises polymer primary particles. A toner for developing an electrostatic charge image, comprising colored particles formed by aggregating and fusing, wherein the degree of crosslinking of the colored particles is from 0.01% by weight to 5% by weight in tetrahydrofuran insoluble matter.
An image forming method, wherein the toner is 0% by weight of an electrostatic image developing toner. 11. An image forming method, comprising: transferring a toner image formed on an image support to a transfer material; and then cleaning the toner remaining on the support, wherein the toner is a polymer primary particle. A toner for developing an electrostatic charge image comprising colored particles formed by aggregation and fusion bonding, wherein the BET specific surface area of the colored particles is 5 m ² / g or more. Item 11. The image forming method according to Item 10. 12. An image forming method, comprising: transferring a toner image formed on an image support to a transfer material, and then cleaning the toner remaining on the support, wherein the toner is polymer primary particles. A toner for developing an electrostatic charge image comprising colored particles formed by aggregation and fusion, which is a toner for developing an electrostatic charge image in which the shape factor of the colored particles is 1.01 to 1.5. The image forming method according to claim 10.