JPH11272010A - Electrostatic charge latent image developing toner and image forming method and image fixing method using the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease changes in the charge amt. of toner particles depending on the environment and to improve hot offset resistance and fixing performance by incorporating resin particles having different mol.wts. each locally present in toner particles and specifying the amts. of carboxyl groups on each surface. SOLUTION: The amt. A [mol/g] of carboxy groups present on the surface of a low mol.wt. component resin, the amt. B [mol/g] of carboxy groups on the surface of a medium mol.wt. component resin, and the amt. C [mol/g] of carboxy groups on the surface of a high mol.wt. component resin satisfy the relation of formulae. These resin components are incorporated in such a manner that from the surface of the toner particle, the medium mol.wt. component resin, the low mol.wt. component resin and the high mol.wt. component resin are successively oriented in this order. Thereby, a three-layer structure of core/intermediate layer/shell is preferably formed, and the effect of each mol.wt. resin on the fixing performance can be effectively used. The amt. of carboxyl groups on the latex surface is controlled by changing the ratio of monomers having carboxyl groups in the monomers added in the polymn. process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, an electrostatic latent image developing toner generally used is prepared by appropriately dry-mixing a colorant such as carbon black, a charge controlling agent and / or a magnetic substance with a polymer obtained by various polymerization methods. After that, it is manufactured by melt-kneading with an extruder or the like, followed by pulverization and classification.

However, the toner obtained by the above-described melt-kneading and pulverizing method has a limitation in controlling the toner particle size, and it is difficult to produce a toner having a small particle size with high yield.

In order to improve the fixing performance of toner,
Although a method using several kinds of binder resins having different molecular weights is known, in the kneading and pulverizing method, it is difficult to control the dispersion state of the binder resin component, and it is difficult to obtain stable fixing performance.

As another method, a method of directly manufacturing a toner by suspension polymerization or the like has been proposed. Also, methods using particles produced by emulsion polymerization have been proposed (for example, JP-A-60-220358, JP-A-4-28).
No. 4461).

However, the direct production method by suspension polymerization is also
Not only is it difficult to reduce the particle size, but the particle size distribution has the disadvantage of being very wide. Further, the toner produced by this method is basically spherical. This spherical toner has the disadvantage that cleaning is difficult in the electrophotographic process.

On the other hand, the methods disclosed in JP-A-60-220358 and JP-A-4-284461 are:
As described above, it is a method that can obtain non-spherical particles having irregularities on the surface instead of a true sphere, but it is difficult to control the particle size and particle size distribution, and the desired particle size and particle size distribution after the reaction is completed. In order to do so, it is necessary to classify. Further, Japanese Patent Laid-Open No. 4-2
In the method disclosed in Japanese Patent No. 84461, it is difficult to adjust the zeta potential of the pigment and the polymer particles. Further, there is a disadvantage that the generated particles cannot have a strong structure and cannot have mechanical strength.

In order to improve the above-mentioned disadvantages, the present inventors have found a method disclosed in Japanese Patent Application Laid-Open No. Hei 6-329947. This method controls the particle size, particle size distribution, chargeability, etc. of non-spherical particles by controlling the degree of dissociation and content of ion-dissociable groups, so that it is easy to control the particle size of non-spherical particles showing high chargeability. However, there is a disadvantage that the controllability of the particle size of the non-spherical particles having low chargeability is reduced.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for developing an electrostatic latent image, in which resin particles having different molecular weights are localized in the toner particles to reduce the difference in the charge amount environment of the toner particles. The purpose is to improve hot offset resistance and fixing performance. Another object of the present invention is to provide toner particles having a small particle size and a narrow particle size distribution.

[0010]

The object of the present invention is achieved by adopting the following constitution.

[1] Low molecular weight component resin latex having a weight average molecular weight of 1,000 to 20,000 as measured by GPC, medium molecular weight component resin latex having a weight average molecular weight of 20,000 to 200,000, weight average In a toner for developing an electrostatic latent image, which is produced by mixing a high molecular weight resin latex having a molecular weight of 200,000 or more, a colorant and a release agent, and aggregating and fusing the toner, the latex is present on the surface of the low molecular weight component resin. The amount of carboxyl groups is A [mol / g], and the amount of carboxyl groups present on the surface of the medium molecular weight component resin is B [m
ol / g], and the following formula is satisfied when the amount of carboxyl groups present on the surface of the high molecular weight component resin is C [mol / g], and the medium molecular weight component resin, the low molecular weight component resin, the high molecular weight A toner for developing an electrostatic latent image, which is oriented in the order of component resins.

0.6 × 10 ⁻⁴ ≦ A ≦ 3.5 × 10 ⁻⁴ (1) 1.0 × 10 ⁻⁴ ≦ B ≦ 4 × 10 ⁻⁴ (2) 0.8 × 10 ⁻⁴ ≦ C ≦ 4 × 10 ⁻⁴ (3) 1 × 10 ⁻⁶ ≦ ^AC ≦ 2 × 10 ⁻⁴ (4) 1 × 10 ⁻⁶ ≦ ^BA ≦ 2 × 10 ⁻⁴ (5) [2] The above low The toner for developing an electrostatic latent image according to [1], wherein the molecular weight resin latex and the high molecular weight resin latex contain an ionic monomer unit having a carboxyl group.

[3] An image forming method for developing an electrostatic latent image formed on a photoreceptor into a toner image, wherein the toner is the toner for developing an electrostatic latent image according to [1]. Image forming method.

[4] An image forming method for transferring a toner image formed on a photoreceptor, wherein the toner is the electrostatic latent image developing toner according to [1].

[5] In an image forming method for transferring a toner image formed on a photoreceptor onto a transfer material and then cleaning and removing the toner remaining on the photoreceptor, the toner according to [1], An image forming method, which is an electrostatic latent image developing toner.

[6] The recording material carrying the visible image obtained by the electrostatic latent image developing toner according to [1] is transported to a heat roller fixing device having a heating roller and a pressure roller. An image fixing method, wherein a toner is pressed and heated and fixed on a recording material by contacting with a heat roller.

In the present invention, the molecular weight of the resin latex was measured by GPC (gel permeation chromatography).

As a result of extensive studies, the present inventors have determined that the amount of carboxyl groups on the surface of each resin latex is as shown in the above formulas (1) to (5), whereby the core / intermediate layer / shell is obtained. It has been found that the three-layer structure is preferably formed and the effect of each molecular weight on the fixing performance can be effectively exerted, and the present invention has been completed.

The toner of the present invention can be formed into three layers, that is, a core, an intermediate layer and a shell, depending on the difference in the amount of carboxyl groups on the surface of each resin latex. The smaller the amount of surface carboxyl groups, the lower the stability of the latex and the stronger the cohesiveness, so that the latex tends to be a core of toner particles. Conversely, the larger the amount of surface carboxyl groups, the higher the hydrophilicity and the more easily the shell.

The amount of carboxyl groups on the surface of the low molecular weight resin latex is 0.6 × 10 ⁻⁴ mol / g or less, and the amount of carboxyl groups on the surface of the medium molecular weight resin latex is 1.
0 × 10 ⁻⁴ mol / g or less, and the amount of carboxyl groups on the surface of the high molecular weight component resin latex is 0.8 × 10 ⁻⁴ mol / g.
If it is less than g, the stability of the latex becomes poor, so that it is difficult to produce a toner having a narrow particle size distribution and a small particle size. Further, the toner cannot have mechanical strength.

When the surface carboxyl group content is 3.5 × 10 ⁻⁴ , 4 × 10 ⁻⁴ , or 4 × 10 ⁻⁴ mol / g or more, the hydrophilicity of the toner particles becomes strong, and the charge amount becomes poor. Become stable.

The difference in the amount of carboxyl groups on the surface between the low molecular weight component resin latex and the high molecular weight component resin latex was 1 × 1
^{0 -6 ≦ A-C ≦ 2} × 10 in the range of ^-4, medium molecular weight component resin latex and a low molecular weight component resin latex surface carboxyl group amount difference of 1 × 10 of ^{-6 ≦ B-A ≦ 2 ×} 10 - By adjusting to the range of ⁴ , toner particles having a phase separation structure and a narrow particle size distribution can be generated.

The present invention will be further described.

(Method of adjusting the amount of carboxyl groups on the surface of latex) The amount of carboxyl groups on the surface of the latex can be adjusted by changing the ratio of the monomer having a carboxyl group in the monomers added during polymerization. Also,
It is also possible by changing the amount of monomer added and the amount of water added during polymerization.

The proportion of the monomer having a carboxyl group in the monomer is preferably 1 to 12 parts, more preferably 2 parts.
To 10 parts.

The amount of the monomer / the amount of the water can be arbitrarily changed, but if the amount of the monomer exceeds the amount of the water, the polymerization does not proceed. The preferred range is 40 /
60 to 3/97, more preferably 35/65.
It is preferable to change it in the range of 5/95.

(Measurement of Carboxyl Group Content on Latex Surface) The carboxyl group content on the surface of latex particles can be measured by titration. In the titration method, a strong base solution such as an aqueous sodium hydroxide solution is used as a titration reagent, and electrical characteristics such as conductivity, pH and the like are used to measure the titration curve. The amount of carboxyl groups on the surface of latex particles is expressed as a value obtained by dividing the amount of carboxyl groups determined by titration by the weight of latex particles, that is, the amount of carboxyl groups per unit latex weight.

(Monomer having a carboxyl group) Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, tetrahydroterephthalic acid, α-alkyl-substituted acrylic acid (substituted alkyl is C1 to C4), monoalkylitaconic acid (substituted alkyl has 1 to 4 carbon atoms), monoalkylmaleic acid (substituted alkyl has 1 to 4 carbon atoms) and the like.

(Resin Latex) As the resin latex, it is generally possible to use an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, an interfacial polymerization method, a fine powder of a synthetic resin, and the like. Are polymer fine particles produced by an emulsion polymerization method.

In order to compound the solid components such as the colorant and the release agent according to the present invention with the resin latex, the solid components according to the present invention can be dispersed in a desired monomer or the solid components can be dissolved. If so, it can be synthesized by dissolving in a monomer, then dispersing in a dispersion, and polymerizing. Further, as described later, after each resin latex is prepared, it can be added when these are coagulated and fused.

These polymer fine particles (resin latex)
The particle size of the target non-spherical particles can be arbitrarily used as long as it is equal to or smaller than the particle size of the intended non-spherical particles. preferable.

(Monomer) In order to obtain the polymer fine particles of the present invention, a hydrophobic monomer is used. Further, a monomer having a carboxyl group is contained as described above.

Examples of the hydrophobic monomer of the present invention include styrene derivatives such as styrene, p-methylstyrene,
o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, p-butoxystyrene,
Examples include 2,4-dimethylstyrene, 2,4-dichlorostyrene, p-chloromethylstyrene, o-chloromethylstyrene, p-hydroxystyrene, o-hydroxystyrene and the like. Also, methyl (meth) acrylate,
Ethyl (meth) acrylates such as ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and dodecyl (meth) acrylate are also included. . Further, nitrile monomers such as acrylonitrile and methacrylonitrile, vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate, olefin monomers such as ethylene, propylene and isobutylene, butadiene and isoprene And conjugated dienes such as chloroprene and dimethylbutadiene. These may be used alone or in combination of two or more as necessary.

These various monomers may be used depending on the purpose.
For example, it is selected according to a desired glass transition temperature, melting temperature, and the like.

(Radical Polymerization Initiator) When synthesizing the polymer fine particles of the present invention, a radical polymerization initiator is selected according to the polymerization method. That is, in the case of the suspension polymerization method, an oil-soluble radical polymerization initiator is used, and in the case of the emulsion polymerization method, a water-soluble radical polymerization initiator is used. Further, in the case of dispersion polymerization, it is appropriately selected depending on the dispersion medium used, but when using a non-aqueous solvent and when using a mixed solvent of a water-miscible organic solvent and water, a water-soluble radical polymerization initiator may be used. It is possible.

Examples of water-soluble radical polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate.
Water-soluble peroxides such as hydrogen peroxide and the like, such as water-soluble azo compounds, for example, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and the like can be mentioned.

Examples of the oil-soluble radical polymerization initiator include:
Oil-soluble peroxides such as benzoyl peroxide, lauroyl peroxide and the like can be mentioned. Examples of the oil-soluble azo polymerization initiator include azobisisobutyronitrile, azobisvaleronitrile and the like. The addition amount of these can be determined according to the molecular weight of the target polymer fine particles and the like. Further, if necessary, a molecular weight regulator, for example, a chain transfer agent represented by a thiol compound, for example, dodecanethiol, octylthiol and the like can be used.

The resin latex according to the present invention has a Tg
Is usually in the range of −10 to 120 ° C., more preferably 0 to 90 ° C. The softening point is 80-220 ° C
Range.

(Solid Component) The resin latex according to the present invention, as described above, is compounded with a colorant and a releasing agent and other solid components added as required.

Examples of the coloring agent include inorganic pigments and organic pigments. Inorganic pigments include carbon pigments such as carbon black, grafted carbon, furnace black, and thermatomic carbon, magnetite, ferrite, red iron oxide, titanium oxide, zinc oxide, silica, chromium oxide, cobalt blue, ultramarine, cerulean blue, and minerals. Metal oxide pigments such as violet and trilead tetroxide; metal powder pigments such as zinc powder, iron powder and copper powder; sulfide pigments such as zinc sulfide, cadmium red, mercury sulfide, selenium red, and cadmium yellow; Examples thereof include chromate pigments such as molybdenum red, barium yellow, stylonium yellow, and chromium yellow, and ferrocyanide pigments such as milori blue.

Particularly, as the inorganic pigment, carbon black, furnace black and the like are preferable.

Examples of the organic pigment include compounds described in Color Index and the like. For example,
As cyan or green pigments, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I.
I. Pigment Blue 15: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

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

As the yellow or orange pigment, C.I.
I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I.
Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 13
8, C.I. I. Pigment Yellow 180 and the like.

Generally, as the organic cyan pigment, C.I.
I. Pigment Blue 15: 3 is known as copper-phthalocyanine, and magenta organic pigments such as C.I. I. Dimethylquinacridone known as CI Pigment Red 122 is C.I. I. Disazo yellow known as CI Pigment Yellow 17 is used.

Further, for example, low-molecular-weight polyethylene, low-molecular-weight polypropylene, oxidized polyethylene, oxidized polypropylene, acid-modified polyethylene, acid-modified polypropylene, polyolefin-based wax (for example, Toho Chemical Industry Co., Ltd.) A release agent such as Hitec Co., Ltd. is used.

Further, a positive charge control agent such as a nigrosine dye, a quaternary ammonium salt, or an alkylamide, an azo-based metal complex, a chlorinated paraffin, a chlorinated polyester,
A negative charge control agent such as sulfonylamine of copper phthalocyanine can be used.

Each of these can be contained in the polymer in an amount of 0.1 to 25% by weight.

(Aggregation / fusion) A toner is produced by aggregation / fusion using the resin latex produced in the polymerization step. Various methods for agglomeration and fusion are available, for example, JP-A-60-220358 and JP-A-4-2844.
There is a method described in JP-A-64-64 and the like. However, it is quite difficult to control the desired particle size and particle size distribution. Therefore, it is desirable to prepare the toner using the method disclosed in JP-A-5-115572, that is, a method in which an organic solvent that is infinitely soluble in water and a coagulant having a concentration equal to or higher than the critical coagulation concentration of the resin latex are added.

(Image Forming Method Used in the Present Invention) FIG. 1 is a sectional view showing an example of a developing device (developing device) used in the image forming method according to the present invention. In this figure, 41
Is a developing sleeve which is a developer carrying body having a fixed magnet 42 therein; 46 is a regulating rod which is a developer carrying amount regulating member; 47 is a scraper which is a developer scraping member;
Is a stirring roller as a developer stirring member, 49 is a casing of the developing device, 50 is a two-component developer composed of toner T and carrier C, 51 is a power supply as bias applying means,
Photosensitive drum which is an image forming body to form a photosensitive layer 12 on the conductive substrate 11, D ₁ is the closest distance between the photosensitive drum 10 the developing sleeve 41, also arrows in FIG. 10 is the photoreceptor Drum 10 and developing sleeve 41
Shows the direction of rotation.

The developing sleeve 41 is made of, for example, aluminum,
It is a cylinder of 0.5 to 3 cm in diameter made of non-magnetic and conductive metal such as stainless steel, and has a surface roughness (Rz) of 1 to 3.
It is processed to be 30 μm. Inside the developing sleeve 41, 4 to 12 magnetized to the N pole or the S pole
A magnet body 42 such as a columnar or split chopstick-shaped (column-shaped) aggregate having magnetic poles is fixedly provided, and the developing sleeve 41 is rotatable with respect to the magnet body 42.

The casing 49 is a casing made of, for example, an insulating resin such as acrylic or polycarbonate. Inside the casing 49, the developing sleeve 41 including the fixed magnet body 42, the supply roller 45, and the scraper 4 are provided.
7 and the stirring roller 48 are disposed,
A regulating rod 46 is disposed at the outlet of the control rod.

A two-component developer 50 composed of toner T and carrier C is stored inside the casing 49. The two-component developer 50 is stirred and mixed by the stirring roller 48 and is supplied by the supply roller 45 and adheres to the developing sleeve 41 to form a magnetic brush. The magnetic brush is transported while the transport amount is regulated by the regulating rod 46 as the developing sleeve 41 rotates.

An AC voltage having a DC component from the power supply 51 is applied to the developing sleeve 41.
A strong oscillating electric field is formed in the gap between the photosensitive drum 10 and the photosensitive drum 10. Due to the strong oscillating electric field, the toner T flies away from the carrier C, and a toner cloud is generated. As a result, a flight toward the latent image on the photosensitive drum 10 occurs, and a toner image is formed on the photosensitive drum 10.

FIG. 2 is a sectional view showing an example of the image forming method of the present invention. In the figure, reference numeral 10 denotes a photosensitive drum as an image forming body, 20 denotes a scorotron charger as charging means,
25 is an image reading unit, 30 is an image writing unit using a laser beam as exposure means, 40A, 40B, 40
Reference numerals C and 40D denote the developing devices shown in FIG. 1 each containing a two-component developer of a different color, 60 denotes a paper feed unit having a first paper feed roller 61 and a second paper feed roller 62, and 70 denotes a transfer unit. A corona charger for transfer; 75, a corona charger for separation as separation means; 80, a transport unit; 85, a fixing unit; 90, a cleaning device including a cleaning blade 91;
Reference numeral 95 denotes a pre-charging exposure lamp. Arrows in the drawing indicate the rotation direction of the photosensitive drum 10.

In the basic operation of the multicolor image forming process according to the present embodiment, first, a copy start command is sent from an operation unit (not shown) to a control unit (not shown), and the photosensitive drum 10 starts rotating. As the photosensitive drum 10 rotates, its peripheral surface is uniformly charged by the scorotron charger 20. In the image reading unit 25, optical information from the document is converted into an electric signal. The electric signal is subjected to image processing and then input to the image writing unit 30. The charged photosensitive drum 10 is irradiated with a laser beam from the image writing unit 30 to form a latent image on the photosensitive drum 10. The latent image on the photosensitive drum 10 is
The toner is developed on any one of the developing devices 40A, 40B, 40C, and 40D, and a toner image is formed on the photosensitive drum 10.

Photosensitive drum 1 on which toner image is formed
0 is uniformly charged again by the scorotron charger 20 and is irradiated with a laser beam by the image writing section 30 to form the next latent image. The latent images on the photosensitive drum 10 are stored in the developing devices 40A, 40B, 40C.
Or 40D, and the next toner image is superimposed on the photosensitive drum 10.

In this embodiment, the latent image forming process described above
The development process is repeated four times, and four color toner images are superimposed on the photosensitive drum 10.

Transfer paper (recording paper), which is a transfer material, is stored in the paper feed unit 60, and the toner is superimposed on the photosensitive drum 10 by the first paper feed roller 61 and the second paper feed roller 62. It is sent to the transfer corona charger 70 in synchronization with the image. The toner image superimposed on the photosensitive drum 10 is transferred onto a recording paper by the transfer corona charger transfer, and the transfer paper is separated from the photosensitive drum 10 by a separating corona charger 75. The transfer paper on which the toner image has been transferred is conveyed to the fixing unit 85 via the conveying unit 80,
After being fused and pressurized and fixed, it is discharged out of the apparatus.

On the other hand, the toner remaining on the photosensitive drum 10 without being transferred to the transfer paper is a cleaning blade 9 pressed against the photosensitive drum 10 at a timed timing.
1 is scraped off by a cleaning device 90 having
After the residual potential is removed by the pre-charging exposure lamp 95,
Enter the next image forming process.

In the development in the present invention, non-contact development is usually performed by applying an AC voltage. In this case, the frequency is preferably 50 to 50,000 Hz.

Here, the order of superposition of color toner images such as yellow, magenta, cyan, and black formed on the surface of the photoreceptor may be any order, but the thickness of the developer layer on the developing sleeve is Dsd because non-contact development is required. Must be smaller.

[0063]

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

[Production of release agent emulsified dispersion] Modified 240 g of low molecular weight polypropylene (number average molecular weight = 3300, molecular weight distribution (Mw / Mn) = 4.5) using 11.4 g of maleic anhydride according to a conventional method. After the melt viscosity was measured, the release agent according to the present invention was nonylphenoxyethanol in which hydrochloric acid was dissolved (the number of moles of ethoxy unit added = 2).
0, HLB = 16.0) aqueous solution, adjusted to pH 9 with potassium hydroxide, pressurized and heated to emulsify and disperse the modified polypropylene above its softening point. The modified polypropylene dispersed particle diameter was measured by a light scattering electric permanent particle diameter measuring apparatus (ELS-800: manufactured by Otsuka Electronics Co., Ltd.), and as a result, was 182 nm. This emulsified dispersion of the release agent was used.

[Preparation of Pigment Dispersion 1] 106.8 g of carbon black (Legal 330R, manufactured by Cabot) was added to 2000 ml of ion-exchanged water and sodium dodecyl sulfate 4 was added.
9.1 g was added, and the mixture was dispersed using an ultrasonic homogenizer and a pressure type disperser. The average particle size of the carbon black in the dispersion was measured using a light scattering electric permanent particle size analyzer (ELS-80).
0: Otsuka Electronics Co., Ltd.).

[Preparation of Pigment Dispersion Liquid 2, 3, 4] Instead of carbon black in Preparation Example of Pigment Dispersion Liquid 1, C.I.
I. Pigment Yellow-17, C.I. I. Pigment Red-122, C.I. I. Pigment Blue-15: 3, except that Pigment Blue-15: 3 was used. The average particle size of the pigment in the dispersion was measured using a light scattering electric permanent particle size analyzer (ELS-800: manufactured by Otsuka Electronics Co., Ltd.).
m and 105 nm.

[Synthesis Example of Low-Molecular-Weight Component Latex 1] A 2-liter 4-tube equipped with a cooling tube, a thermometer, a stirrer, and a nitrogen inlet tube
1080 ml of distilled water was added to the head flask, and 236.8 g of styrene and 70.4 g of n-butyl acrylate were added thereto.
g, 12.8 g of methacrylic acid, 11.0 g of tert-dodecyl mercaptan, and 64 g of an emulsified dispersion of a release agent were further added. . While maintaining the internal temperature at 70 ° C., 3.28 g of potassium persulfate was added to pure water 2
An aqueous solution of the polymerization initiator dissolved in 00 ml was added, and polymerization was carried out for 6 hours while maintaining an internal temperature of 70 ° C. and a stirring speed of 220 rpm under a nitrogen stream.

After the polymerization, the internal temperature was lowered to room temperature,
The molecular weight was measured using a part of the gel permeation chromatography (hereinafter abbreviated as GPC).

The surface carboxyl group content of the low molecular weight component latex was measured by conductivity titration.

In the conductivity titration, the latex was diluted to a solid concentration of 5% by weight, and a 0.05N aqueous solution of sodium hydroxide was added dropwise at intervals of 15 seconds in 0.5 ml portions. Use to generate a titration curve.
The inflection point was determined from the titration curve to determine the amount of carboxyl groups on the surface of the latex.

[Synthesis Example of Low-Molecular-Weight Component Latex 2] The synthesis example of low-molecular-weight component latex 1 was the same except that the amount of added monomer was changed to 230.4 g of styrene and 19.2 g of methacrylic acid.

[Synthesis Example of Low-Molecular-Weight Component Latex 3] The procedure was the same as in the synthesis example of low-molecular-weight component latex 2, except that the amount of added monomer was 229.6 g and methacrylic acid was 20.0 g.

[Synthesis Example of Low-Molecular-Weight Component Latex 4] The synthesis example of low-molecular-weight component latex 1 was the same except that the amount of monomer added was changed to 224.0 g of styrene and 25.6 g of methacrylic acid.

The molecular weight of the low molecular weight component latexes 1-4,
The amount of surface carboxyl groups is shown below.

[0075]

[Table 1]

[Synthesis Example of Medium Molecular Weight Component Latex 1] One liter of 4 equipped with a cooling tube, thermometer, stirrer, and nitrogen inlet tube
540 ml of distilled water was added to the head flask, and 115.2 g of styrene and 36.8 n-butyl acrylate were added thereto.
g, 8.0 g of methacrylic acid, 4.0 g of tert-dodecyl mercaptan, and 32 g of an emulsified dispersion of a release agent were further added. . While maintaining the internal temperature at 70 ° C., 1.64 g of potassium persulfate was added to pure water 10
An aqueous solution of the polymerization initiator dissolved in 0 ml is added, and while maintaining the internal temperature at 70 ° C. and the stirring speed at 350 rpm under a nitrogen stream, 6
Polymerization was carried out for hours.

The molecular weight and the amount of carboxyl groups on the surface of the latex were measured in the same manner as in the synthesis example of the low molecular weight component latex 1.

[Synthesis Example of Medium Molecular Weight Component Latex 2] The same procedure as in the synthesis example of medium molecular weight component latex 1 was carried out except that the amount of added monomer was changed to 113.6 g of styrene and 9.6 g of methacrylic acid.

[Synthesis Example of Medium Molecular Weight Component Latex 3] The same procedure as in the synthesis example of Medium Molecular Weight Component Latex 1 was carried out except that the amount of added monomer was changed to 112.8 g of styrene and 10.4 g of methacrylic acid.

[Synthesis Example of Medium Molecular Weight Component Latex 4] The same procedure as in the synthesis example of medium molecular weight component latex 1 was carried out except that the amount of monomer added was changed to 110.4 g of styrene and 12.8 g of methacrylic acid.

[Synthesis Example of Medium Molecular Weight Component Latex 5] The same procedure as in the synthesis example of medium molecular weight component latex 1 was performed except that the amount of monomer added was changed to 104.04 g of styrene and 19.2 g of methacrylic acid.

The molecular weight of the middle molecular weight component latex 1-5,
The amount of surface carboxyl groups is shown below.

[0083]

[Table 2]

[Synthesis Example of High Molecular Weight Component Latex 1] One liter of 4 equipped with a cooling tube, thermometer, stirrer, and nitrogen inlet tube
To a head flask, 540 ml of distilled water was added, and 120.0 g of styrene and 38.4 n-butyl acrylate were added thereto.
g, 1.6 g of methacrylic acid, 0.10 g of tert-dodecyl mercaptan, and 32 g of an emulsified dispersion of a release agent. The mixture is stirred at a stirring speed of 350 rpm and heated to 70 ° C. while flowing nitrogen while flowing nitrogen. did. While maintaining the internal temperature at 70 ° C., 1.64 g of potassium persulfate was added to pure water 1
A polymerization initiator aqueous solution dissolved in 00 ml was added, and polymerization was carried out for 6 hours while maintaining an internal temperature of 70 ° C. and a stirring speed of 350 rpm under a nitrogen stream.

The molecular weight and the amount of carboxyl groups on the surface of the latex were measured in the same manner as in the synthesis example of the low molecular weight component latex 1.

[Synthesis example of high-molecular-weight component latex 2] The same procedure as in the synthesis example of high-molecular-weight component latex 1 was carried out except that the amount of added monomer was changed to 118.4 g of styrene and 3.2 g of methacrylic acid.

[Synthesis Example of High Molecular Weight Component Latex 3] The same procedure as in the synthesis example of high molecular weight component latex 1 was carried out except that the amount of monomer added was changed to 112.0 g of styrene and 9.6 g of methacrylic acid.

[Synthesis Example of High Molecular Weight Component Latex 4] The same procedure as in the synthesis example of high molecular weight component latex 1 was carried out except that the amount of monomer added was changed to 110.4 g of styrene and 11.2 g of methacrylic acid.

High molecular weight component Molecular weight of latex 1-4,
The amount of surface carboxyl groups is shown below.

[0090]

[Table 3]

[Toner Synthesis Example 1] Low-molecular-weight latex surface carboxyl group amount A = 2.02 × 10 ⁻⁴ , medium-molecular latex surface carboxyl group amount B = 2.57 × 10 ⁻⁴ , high-molecular latex surface carboxyl group amount C = 1.26 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 3, 100 g of the medium molecular component latex 3, 100 g of the high molecular component latex 3, 160 g of the pigment dispersion 1, and 340 ml of ion-exchanged water using a 5N aqueous solution of sodium hydroxide were used.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 57.62 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. The coefficient of variation (CV) of the toner is a value obtained by dividing the standard deviation σ by the volume average particle diameter d ₅₀ . This toner is referred to as toner 1.

[Toner Synthesis Example 2] Low-molecular latex surface carboxyl group content A = 1.13 × 10 ⁻⁴ , medium molecular latex surface carboxyl group content B = 1.69 × 10 ⁻⁴ , polymer latex surface carboxyl group content C = 0.62 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 2, 100 g of the medium molecular component latex 1, 100 g of the high molecular component latex 2, 160 g of the pigment dispersion 1, and 340 ml of ion-exchanged water were adjusted to pH using a 5N aqueous sodium hydroxide solution.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 54.24 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 2.

[Toner Synthesis Example 3] Low-molecular latex surface carboxyl group content A = 3.32 × 10 ⁻⁴ , medium molecular latex surface carboxyl group content B = 3.85 × 10 ⁻⁴ , high-molecular latex surface carboxyl group content C = 2.78 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 4, 100 g of the medium molecular component latex 4, 100 g of the high molecular component latex 4, 160 g of the pigment dispersion 1, and 340 ml of ion-exchanged water were adjusted to pH using a 5N aqueous sodium hydroxide solution.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, sodium chloride 59.66 g
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 3.

[Toner Synthesis Example 4] Amount of carboxyl groups on the surface of low molecular latex A = 2.02 × 10 ⁻⁴ , amount of carboxyl groups on medium molecular latex B = 3.85 × 10 ⁻⁴ , amount of carboxyl groups on polymer latex C = 0.62 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 3, 100 g of the medium molecular component latex 4, 100 g of the high molecular component latex 2, 160 g of the pigment dispersion 1, and 340 ml of ion-exchanged water were adjusted to pH using a 5N aqueous sodium hydroxide solution.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, sodium chloride 59.66 g
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse the solution.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 4.

[Toner Synthesis Example 5] Low-molecular-weight latex surface carboxyl group amount A = 1.95 × 10 ⁻⁴ , medium-molecular latex surface carboxyl group amount B = 2.57 × 10 ⁻⁴ , high-molecular latex surface carboxyl group amount C = 1.26 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 2, 100 g of the medium molecular component latex 3, 100 g of the high molecular component latex 3, 200 g of the pigment dispersion 2, and 300 ml of ion-exchanged water using a 5N aqueous solution of sodium hydroxide.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 55.58 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse the solution.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 5.

[Toner Synthesis Example 6] Low-molecular-weight latex surface carboxyl group amount A = 1.95 × 10 ⁻⁴ , medium-molecular latex surface carboxyl group amount B = 2.57 × 10 ⁻⁴ , high-molecular latex surface carboxyl group amount C = 1.26 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 2, 100 g of the medium molecular component latex 3, 100 g of the high molecular component latex 3, 160 g of the pigment dispersion 3, and 340 ml of ion-exchanged water using a 5N aqueous sodium hydroxide solution were used to adjust the pH.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 56.94 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After filtering the reaction solution, distilled water was added to re-disperse the solution,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 6.

[Toner Synthesis Example 7] Amount of carboxyl group on the surface of low molecular latex A = 1.95 × 10 ⁻⁴ , amount of carboxyl group on medium molecular latex B = 2.57 × 10 ⁻⁴ , amount of carboxyl group on polymer latex C = 1.26 × 10
Example of toner production using a combination of latex- ⁴ .

300 g of the low molecular component latex 2, 100 g of the medium molecular component latex 3, 100 g of the high molecular component latex 3, 80 g of the pigment dispersion 4 and ion-exchanged water 4
20 ml of a 5N aqueous solution of sodium hydroxide was used to adjust pH =
After adjusting to 9.5, the mixture was placed in a 2-liter four-headed flask equipped with a stirrer, a cooling pipe and a temperature sensor, and stirred at 156 rpm. To this, an aqueous electrolyte solution obtained by dissolving 54.24 g of sodium chloride in 280 ml of distilled water was added.
Further, 104 ml of isopropyl alcohol, Triton X-
After sequentially adding an aqueous nonionic surfactant solution in which 90 g of 100 was dissolved in 80 ml of distilled water, the internal temperature was raised to 85 ° C., and the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse the solution.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as toner 7.

[Comparative Toner Synthesis Example 1] Low-molecular latex surface carboxyl group content A = 2.02 × 10 ⁻⁴ , medium molecular latex surface carboxyl group content B = 2.02 × 10 ⁻⁴ ,
Carboxyl group content of polymer latex surface C = 1.26 ×
Example of toner production using a combination of 10 ^-4 latex.

300 g of the low-molecular component latex 3, 100 g of the medium-molecular component latex 2, 100 g of the high-molecular component latex 3, 160 g of the pigment dispersion 1, and 340 ml of ion-exchanged water were adjusted to pH using a 5N aqueous sodium hydroxide solution.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 56.94 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse the solution.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as comparative toner 1.

[Comparative Toner Synthesis Example 2] Toner production of a combination of a latex having a low-molecular latex surface carboxyl group content A = 2.02 × 10 ⁻⁴ and a high-molecular latex surface carboxyl group content C = 2.78 × 10 ⁻⁴ Example.

400 g of the low molecular component latex 3, 100 g of the high molecular component latex 4, and 160 g of the pigment dispersion 1
g and 340 ml of ion-exchanged water were adjusted to pH = 9.5 using a 5N aqueous sodium hydroxide solution, and then placed in a 2-liter four-necked flask equipped with a stirrer, a cooling tube and a temperature sensor, and stirred at 156 rpm. . To this, an aqueous electrolyte solution obtained by dissolving 58.3 g of sodium chloride in 280 ml of distilled water was added.
l, 9.0 g of Triton X-100 was dissolved in 80 ml of distilled water, and an aqueous solution of nonionic surfactant was sequentially added.
The internal temperature was raised to 85 ° C., and the reaction was performed for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse the solution.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as Comparative Toner 2.

[Comparative Toner Synthesis Example 3] Toner production of a combination of a latex having a low-molecular latex surface carboxyl group amount A = 3.32 × 10 ⁻⁴ and a high-molecular latex surface carboxyl group amount C = 2.78 × 10 ⁻⁴ Example.

400 g of the low molecular component latex 4, 100 g of the high molecular component latex 4 and 160 g of the pigment dispersion 1
g and 340 ml of ion-exchanged water were adjusted to pH = 9.5 using a 5N aqueous solution of sodium hydroxide, and then placed in a 2-liter four-headed flask equipped with a stirrer, a condenser, and a temperature sensor, and stirred at 156 rpm. . To this, an aqueous electrolyte solution obtained by dissolving 58.98 g of sodium chloride in 280 ml of distilled water was added.
ml, 9.0 g of Triton X-100 in 80 ml of distilled water
After sequentially adding a nonionic surfactant aqueous solution dissolved in the above, the internal temperature was raised to 85 ° C., and the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as comparative toner 3.

[Comparative Toner Synthesis Example 4] Amount of carboxyl groups on the surface of low molecular latex A = 1.13 × 10 ⁻⁴ , amount of carboxyl groups on medium molecular latex B = 1.69 × 10 ⁻⁴ ,
Carboxyl group content of polymer latex surface C = 0.55 ×
Example of toner production using a combination of 10 ^-4 latex.

300 g of the low molecular weight component latex 1, 100 g of the medium molecular weight latex 1, 100 g of the high molecular weight latex 1, 160 g of the pigment dispersion 1 and 340 ml of ion-exchanged water using a 5N aqueous sodium hydroxide solution were used.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, 52.88 g of sodium chloride
Was added to 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was successively added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added for redispersion.
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as comparative toner 4.

[Comparative Toner Synthesis Example 5] Low-molecular-weight latex surface carboxyl group content A = 3.32 × 10 ⁻⁴ , medium-molecular latex surface carboxyl group content B = 4.31 × 10 ⁻⁴ ,
Polymer latex surface carboxyl group content C = 2.78 ×
Example of toner production using a combination of 10 ^-4 latex.

300 g of the low molecular weight component latex 4, 100 g of the middle molecular weight latex 5, 100 g of the high molecular weight latex 4, 160 g of the pigment dispersion 1 and 340 ml of ion-exchanged water were adjusted to pH using a 5N aqueous sodium hydroxide solution.
= 9.5, put into a 2 l four-headed flask equipped with a stirrer, cooling tube and temperature sensor, and set to 156 rpm
With stirring. Here, sodium chloride 65.76 g
Was dissolved in 280 ml of distilled water, an aqueous solution of nonionic surfactant in which 104 ml of isopropyl alcohol and 9.0 g of Triton X-100 were dissolved in 80 ml of distilled water was sequentially added.
And the reaction was carried out for 6 hours.

After the reaction solution was filtered, distilled water was added to re-disperse,
After adjusting the pH to 13 using a 5N aqueous sodium hydroxide solution, washing with water and filtration were repeated to remove the surfactant and the electrolyte, drying was performed. After drying, the particle size was measured using a Coulter counter. This toner is referred to as comparative toner 5.

Table 4 shows the particle diameter, standard deviation, and coefficient of variation of each of the toners 1 to 7 and the comparative toners 1 to 5.

[0128]

[Table 4]

Evaluation 1 Environmental Difference of Charge Amount Toners 1 to 7 of the present invention and Comparative Toners 1 to 5 were mixed with 100 parts by weight of 2 parts by weight of hydrophobic silica and 1 part by weight of titanium oxide. 5 parts by weight of this externally added toner and methyl methacrylate / styrene copolymer (MAA)
/ St = 7/3 weight ratio), and 95 parts by weight of ferrite particles (carrier, average particle size 60 μm) surface-coated with
Developers 1 to 7 of the present invention and Comparative developers 1 to 5 were used. The charge amount when the developer was shaken with a shaker for 60 minutes was measured by a blow-off method. The measurement was performed at low temperature and low humidity (LL:
10 ° C., 20% RH), high temperature and high humidity (HH: 33 ° C., 80)
% RH), and the difference in charge amount between LL and HH was taken as the environmental difference.

Evaluation 2 Anti-Hot Offset Performance Konica color copier Konica manufactured using the above developer with a fixing roller temperature fixed at 180 ° C.
9028 was modified and a hot offset resistance test was performed. The conditions are as shown below. A laminated organic photoreceptor was used as the photoreceptor.

Photoconductor surface potential = -550 V DC bias = -250 V AC bias = Vp-p: -50 to -450 V Alternating electric field frequency = 1800 Hz Dsd (distance between photoconductor and developing sleeve) = 300 μm Pressing force = 10 gf / mm Pressure regulating rod = SUS416 (made of magnetic stainless steel) / diameter 3 mm Developer layer thickness = 150 μm Developing sleeve = 20 mm 100 sheets were continuously copied under the above conditions, and the presence or absence of hot offset was visually determined. The evaluation was “○” when no hot offset was observed and “×” when hot offset was observed.

Evaluation 3 Fixing Performance Konica Color Copier K using a developer having a fixing roller temperature fixed at 180 ° C. and the developer described in Evaluation 1 was used.
An image was obtained using the same method as described in Evaluation 2 of Sonica 9028. The image was rubbed with a bleached cotton cloth, and the change in reflection density before and after rubbing was measured as a fixing rate. The fixing rate was calculated as (reflection density after rubbing / reflection density before rubbing).

Evaluations were as follows: fixing rate 70% or more: good (good), 7
Less than 0% was evaluated as x (problem).

[0134]

[Table 5]

As is evident from the results shown in Table 5, the toner of the present invention has good charge amount environment difference, offset resistance, and fixing performance, while the toner of the present invention has at least one of the characteristics. It turns out there is a problem.

[0136]

According to the present invention, in a toner for developing an electrostatic latent image, resin particles having different molecular weights are localized in the toner particles, thereby reducing the difference in charge amount environment of the toner particles, hot offset resistance, and fixing performance. Can be improved. Further, toner particles having a small particle size and a narrow particle size distribution can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a developing device according to the present invention.

FIG. 2 is a cross-sectional view illustrating an example of the image forming method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 photoconductor drum (image forming body) 11 conductive substrate 12 photosensitive layer 20 scorotron charger 25 image reading unit 30 image writing unit 40A, 40B, 40C, 40D developing device (developing device) 41 developing sleeve (developer conveying member) 42 magnet body 45 supply roller 46 regulating rod 47 scraper 48 stirring roller 49 casing 50 two-component developer 51 power supply 60 paper supply unit 61 first paper supply roller 62 second paper supply roller 70 transfer corona charger 75 separation corona charger Container 80 Conveying Unit 85 Fixing Unit 90 Cleaning Device 91 Cleaning Blade 95 Pre-Charge Exposure Lamp

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yoshiki Nishimori 1st Sakuracho, Hino-shi, Tokyo Konica Corporation In-house (72) Inventor Mikio Kamiyama 1st Sakuracho, Hino-shi, Tokyo In-house Konica Corporation

Claims (6)

[Claims] 1. A low molecular weight component resin latex having a weight average molecular weight of 1,000 to 20,000 as measured by GPC, a medium molecular weight component resin latex having a weight average molecular weight of 20,000 to 200,000, and a weight average molecular weight In a toner for developing an electrostatic latent image formed by mixing, aggregating and fusing, a high molecular weight component resin latex, a colorant and a release agent of 200,000 or more, the carboxyl present on the surface of the low molecular weight component resin The amount of the group was A [mol / g], and the amount of the carboxyl group present on the surface of the medium molecular weight component resin was B [mol / g].
g], when the amount of carboxyl groups present on the surface of the high molecular weight component resin is C [mol / g], the following formula is satisfied, and from the particle surface, the medium molecular weight component resin, the low molecular weight component resin, and the high molecular weight component resin A toner for developing an electrostatic latent image. 0.6 × 10 ⁻⁴ ≦ A ≦ 3.5 × 10 ⁻⁴ (1) 1.0 × 10 ⁻⁴ ≦ B ≦ 4 × 10 ⁻⁴ (2) 0.8 × 10 ⁻⁴ ≦ C ≦ 4 × 10 ^-4 (3) 1 × 10 ^-6 ≤AC≤2 × 10 ^-4 (4) 1 × 10 ^-6 ≤BA≤2 × 10 ^-4 (5) 2. The toner for developing an electrostatic latent image according to claim 1, wherein the low molecular weight resin latex and the high molecular weight resin latex contain an ionic monomer unit having a carboxyl group. 3. An image forming method for developing a latent electrostatic image formed on a photoreceptor to form a toner image, wherein the toner is the toner for developing a latent electrostatic image according to claim 1. Image forming method. 4. An image forming method for transferring a toner image formed on a photoreceptor, wherein the toner is the toner for developing an electrostatic latent image according to claim 1. 5. The image forming method according to claim 1, wherein the toner image formed on the photoconductor is transferred onto a transfer material, and the toner remaining on the photoconductor is cleaned and removed. An image forming method, which is a toner for developing a latent charge image. 6. A recording material carrying a visible image obtained by the electrostatic latent image developing toner according to claim 1 is conveyed to a heat roller fixing device having a heating roller and a pressure roller. An image fixing method, wherein a toner is pressed and heated and fixed on a recording material by contacting with a heat roller.