JP3069938B2 - Electrostatic image developing toner and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerized toner used for visualizing an electrostatic latent image in electrophotography and the like, and a method for producing the toner.

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat.
As described in, for example, US Pat. No. 691 and the like, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using toner, and if necessary, the toner image is transferred to a transfer member such as paper, and then is fixed by heating, pressing, or solvent vapor to obtain a copy. Further, as a method of developing using a toner or a method of fixing a toner image, various methods have been conventionally proposed, and a method suitable for each image forming process is adopted.

Conventionally, toners used for these purposes are generally prepared by melt-mixing a coloring agent composed of a dye and a pigment in a thermoplastic resin, uniformly dispersing the same, and then using a pulverizer or a classifier to obtain a toner having a desired particle size. Has been manufactured.

[0004] Toners produced by this production method are required to have good meltability when heat is applied due to production restrictions, and to have a low softening point, a low melt viscosity and a high sharp melt property. You.

However, such a toner having a high sharp melt property has a high affinity for a fixing roller of an image forming apparatus or the like, and tends to be easily offset to the fixing roller at the time of fixing.

Therefore, conventionally, a releasing agent such as silicone oil has been applied to the fixing roller to improve the releasability of the toner from the fixing roller. However, such an image forming method has the following disadvantages.

That is, in the current fixing system in which a release agent such as oil is applied to the roller, not only the structure of the image forming apparatus main body becomes complicated, but also the oil application shortens the life of the fixing roller. The negative effect of promoting it follows.

[0008] In recent years, with various needs for copying,
Although the passage of film-like resin and the like has begun to be widely performed, generally, a film for overhead projectors, also known as a transparency film, is well known, but in such a fixing method, the stickiness due to oil application can be avoided. However, a major problem remains in the quality of the obtained image. On the other hand, with the speeding up of the copying machine and further energy saving, further low-temperature fixability and offset resistance of the toner are required.

With respect to such a problem, there has been great expectation for establishing a fixing system that does not require oil application and developing a new toner for achieving the fixing system.

To solve the above-mentioned problems, a toner containing a release agent such as wax or a suspension polymerization method toner has been proposed (Japanese Patent Publication No. 36-10231). In this suspension polymerization method, a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are uniformly dissolved or dispersed to form a monomer composition. After that, the monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer by using a suitable stirrer, and simultaneously undergoes a polymerization reaction, whereby toner particles having a desired particle size are obtained. What you get.

In this suspension polymerization method, droplets of the monomer composition are formed in a highly polar dispersion medium called water.
The component having a polar group contained in the monomer composition has a so-called core / shell structure in which a component having a polar group is easily present in a surface layer which is an interface with an aqueous phase, and a nonpolar component is not present in the surface layer. By utilizing the characteristics of this production method, it is possible to contain a low melting point wax which cannot be used in other pulverization methods.

By incorporating the low-melting-point wax into the toner by the polymerization method, it is possible to achieve both of the contradictory performances of blocking resistance and low-temperature fixability. That is, since the low melting point wax is included, the thermal conductivity in the toner is improved by the wax that melts at a low temperature without lowering the blocking resistance, and as a result,
Low-temperature fixing becomes possible. Still more preferably,
Since the wax melted at the time of fixing also works as a release agent,
Without applying a release agent such as oil to the fixing roller,
High-temperature offset can be prevented.

The core / shell structure has already been confirmed from a dyed TEM photograph of the cut surface of the toner.

However, recently, when the outermost layer of the polymerized toner containing a large amount of wax was measured by XPS in order to obtain good fixability, the wax content ratio in the toner surface component was 5%. % By weight.

The presence of the wax on the surface of the toner contaminates the developing sleeve, the photosensitive drum, the transfer drum, and the like, and causes a reduction in durability.

As a method for removing contaminants present on the surface of the toner, the toner recovered after the polymerization is treated with an organic solvent that does not dissolve the binder resin.
Method for removing residual dispersion stabilizer and contaminants (Japanese Unexamined Patent Publication No.
No. 45768) and a method of removing a residual dispersion stabilizer with a water-soluble organic solvent which does not dissolve the binder resin (Japanese Patent Laid-Open No. Hei.
No. 64652). However, these methods have problems that the removal step is complicated and that the wax cannot be removed even if the step is easy.

[0017]

SUMMARY OF THE INVENTION The present inventor has reported that in suspension polymerization in an aqueous medium, polar components are concentrated near the interface and non-polar components are concentrated in the central part. Developed a polymerized toner containing a large amount of wax components that cannot be manufactured by a toner manufacturing method that relies on kneading and pulverization, and developing a toner that can be fixed at a low temperature and does not require the application of a release agent to the fixing device during fixing. Obtained.

However, if a large amount of low-melting wax is contained in the polymerized toner system, a high-quality image can be obtained without any problem under a normal environment. Due to contamination and the like, a phenomenon that durability under high temperature and high humidity was significantly reduced occurred.

An object of the present invention is to provide a toner for developing an electrostatic image which has solved the above-mentioned problems.

It is another object of the present invention to provide a toner for developing an electrostatic image, which is fixed at a low temperature, has excellent releasability, and has excellent blocking resistance.

It is a further object of the present invention to provide a method for removing the contaminants on the toner surface by a simple method to produce the toner for developing an electrostatic image.

[0022]

Means and operation for solving the problems] The present invention made to achieve the above object, a polymerizable monomer, a colorant and the
A polymerization step of subjecting a monomer composition containing at least 10 to 40 parts by weight of a releasing agent to 100 parts by weight of the polymerizable monomer to suspension polymerization in an aqueous medium , and the polymerization step being completed After, suspension
Add a surface modifying liquid to the toner to remove the release agent from the toner surface.
In the method for producing a polymerized toner for developing an electrostatic charge image having at least a removing step , the obtained toner has a toner surface
A method for producing a toner for developing an electrostatic image, characterized in that the abundance ratio of a release agent in the component is less than 5% by weight , and further a toner for developing an electrostatic image, obtained by this method.

Hereinafter, the present invention will be described specifically.

The inventors of the present invention have conducted intensive studies on a method for producing a polymerized toner, and have found that the durability under high temperature and high humidity can be significantly improved by removing the release agent on the toner surface after the polymerization step. The present invention has been completed.

In the present invention, the release agent on the toner surface is removed by combining a surfactant, an organic acid, an organic acid salt, an aliphatic amine derivative, a water-soluble organic solvent, potassium hydroxide, phosphoric acid, and pure water. It is performed by adding the surface modification liquid after the completion of the polymerization step. Specific examples of this surface modification liquid include:
SC CLEANER- made by Diaflock Inc.
7, SC CLEANER-B, SC CLEANER
-D, STRIPPER-Q / O, OAKITE-33
Etc.

Specific examples of each component of the surface-modifying liquid are shown below, but the present invention is not limited thereto.

As the organic acid salt, a salt obtained from carboxylic acid, sulfonic acid, sulfinic acid, phenolic acid or the like is used.

Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, butanol, isobutanol, tert-butanol, hexanol and octanol, dioxane, dimethyl ether, and the like.
Ethers such as diethyl ether, tetrahydrofuran, ethylene glycol, monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ketones such as acetone methyl ethyl ketone and cyclohexanone, formamide, dimethylformamide, acetonitrile and the like are used.

Examples of the aliphatic amine derivatives include aliphatic primary amines such as methylamine, ethylamine and propylamine; aliphatic secondary amines such as dimethylamine, diethylamine and dipropylamine; and aliphatic tertiary amines such as trimethylamine and triethylamine. Use is made of aliphatic unsaturated amines such as amine, allylamine, diallylamine, triallylamine and derivatives thereof.

As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant, which are mainly water-soluble surfactants, are used. In addition, any oil-soluble surfactant may be used as long as it is soluble in water.

In the present invention, the use temperature of the surface modifying liquid is not particularly limited, but is preferably 60 ° C.
~ 80 ° C is desired. The timing of adding the surface modification liquid is not particularly limited as long as it is after the completion of the polymerization reaction, and may be before or after removing the dispersion stabilizer or the like.

The surface treatment time after the addition is not particularly limited.

The present inventors have shown that the addition of the above-mentioned surface modifying liquid after the completion of the polymerization step can reduce the abundance ratio of the release agent in the toner surface component to less than 5% by weight by XPS (X-ray photoelectron spectroscopy). Method) to confirm the toner surface. Therefore, when the toner of the present invention is used in a copying machine or the like, the durability particularly under high temperature and high humidity is improved, and a good image can be stably obtained over a long period of time. In addition, regarding the durability, if the abundance ratio of the release agent is less than 2.0% by weight, there is a remarkable effect.

In the present invention, the analysis of the toner surface by the XPS can be exemplified by the following measuring apparatus and measuring conditions.

(Apparatus) ESCALAB5 manufactured by VG (Measurement conditions)

[0036]

[Outside 1] X-ray output; 8 kV, 20 mA Analyzer mode; constant analaz
eenerergy (CAE) modepass e
energy wide scan50eV, narr
ow scan 20 eV resolution; Ag3d _5/2 FWHM = 1.0 eV slit; A4 degree of vacuum; 1 × 10 ^-9 Torr horizontal axis correction; neutral carbon C1s peak value 284.6 eV
I made it.

In the present invention, the content of the release agent is from 10 to 40 parts by weight, more preferably from 10 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer. When the content of the releasing agent is less than 10 parts by weight, the releasing effect of the toner is deteriorated and the offset resistance is deteriorated. On the other hand, if the content of the release agent exceeds 40 parts by weight, the granulation property during production deteriorates, and the blocking property of the obtained toner also deteriorates.

The melting point of the release agent according to the present invention is 30.
To 150 ° C., more preferably 50 to 150 ° C.
100 ° C. When the melting point is lower than 30 ° C., the blocking resistance and shape retention of the toner are not sufficient.
When the temperature is higher than 50 ° C., the effect of the releasability is not sufficient.
The melting point was the temperature of the maximum endothermic peak by DSC.

The waxes used in the present invention include:
Paraffin / polyolefin waxes and their modified products, such as oxides and grafted products, higher fatty acids and their metal salts, amide waxes, and ester waxes, such as tertiary and / or quaternary carbon And a polyfunctional polyester compound obtained from a difunctional or higher alcohol compound or a carboxylic acid compound, and a polyfunctional compound having a primary or / and secondary carbon and obtained from a difunctional or higher alcohol compound or a carboxylic acid compound Examples thereof include a polyester compound and a monofunctional ester compound having a tertiary or / and quaternary carbon.

Examples of the polymerizable monomer that can be used in the present invention include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene. , Methyl acrylate, ethyl acrylate, n-butyl acrylate
Acrylic esters such as isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, Ethyl methacrylate / n-propyl methacrylate / n-butyl methacrylate / isobutyl methacrylate / n-octyl methacrylate / dodecyl methacrylate / 2-ethylhexyl methacrylate / stearyl methacrylate / phenyl methacrylate / dimethylaminoethyl methacrylate Examples include methacrylic acid esters such as diethylaminoethyl methacrylate and other monomers such as acrylonitrile, methacrylonitrile and acrylamide. These monomers alone,
Alternatively, they can be used in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in a mixture with another monomer, from the viewpoint of the developing characteristics and durability of the toner.

In the present invention, it is more preferable to polymerize the monomer system by adding a polymer / copolymer having a polar group as an additive. The polar polymer / copolymer gathers on the surface layer of the toner particles, so that it forms a kind of shell, which gives the toner particles excellent properties such as anti-blocking properties, while comparing inside the toner. By performing polymerization so as to contribute to improvement of fixing characteristics at a very low molecular weight, a toner satisfying conflicting requirements of fixing property and blocking resistance can be obtained. The polar polymers and copolymers that can be used in the present invention are exemplified below.

Polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, copolymers with styrene / unsaturated carboxylic acid esters, etc., nitrile monomers such as acrylonitrile, and vinyl chloride Halogen-containing monomers, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids
Unsaturated dibasic acid anhydrides, polymers such as nitro monomers or copolymers with styrene monomers, polyesters,
Epoxy resins and the like can be mentioned. Particularly, it is preferable to add a polyester resin from the viewpoint of maintaining the core / shell structure. The amount of the polar polymer / copolymer added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymerizable monomer.

As the colorant used in the present invention, known colorants can be used, for example, carbon black, C.I.
I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 9, C.I. I. Acid blue 15,
C. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. Dyes such as Basic Green 6, graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, Permanent red 4
R, Watching red calcium salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Malachite Green Rake, Final Yellow Green G and the like.
In the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the aqueous phase migration property of the colorant, preferably, surface modification, for example, hydrophobicity by a substance without polymerization inhibition It is better to have a chemical treatment. In particular,
Since many dyes and carbon blacks have polymerization inhibitory properties, care must be taken when using them. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system.

The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane, in addition to the same treatment as the above dye.

When a color toner is used, it is desirable to select and use a disazo yellow pigment, a quinacridone magenta pigment, or a phthalocyanine cyan pigment.

When the toner is used as a magnetic toner, it may contain a magnetic powder. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used.
There are powders of ferromagnetic metals such as iron, cobalt and nickel, or compounds such as magnetite and ferrite. In particular, in the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory properties and aqueous phase migration properties of the magnetic substance, preferably, surface modification, for example, without polymerization inhibition It is better to carry out a hydrophobic treatment with a substance.

In the present invention, it is desirable to add a charge control agent to the toner material in order to control the chargeability of the toner. As these charge control agents, those having little polymerization inhibition and water phase transfer among known ones are used. For example, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidines Derivatives, imidazole derivatives, amine-based and polyamine-based compounds, and the like, as negative charge control agents, metal-containing salicylic acid-based compounds, metal-containing monoazo-based dye compounds, urea derivatives, styrene-acrylic acid copolymers, styrene-methacrylic Acid copolymers and the like can be mentioned. The addition amount of these charge control agents is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymerizable monomer.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-
Azo or diazo polymerization initiators such as carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-zochlorobenzoyl peroxide and lauroyl peroxide are exemplified. These polymerization initiators include the polymerizable monomer 10
The addition amount is preferably 0.5 to 20 parts by weight with respect to 0 parts by weight, and may be used alone or in combination.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight. The preferable addition amount is 0.1 to 100 parts by weight of the polymerizable monomer. 001 to 15 parts by weight.

The additives used in the present invention for imparting various toner properties include those having a volume average diameter of 1/5 or less of the toner particles from the viewpoint of durability when added to the toner or when added to the toner. Preferably it is a particle size. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these properties, for example, the following are used.

1) Fluidity imparting agents: metal oxides (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Those subjected to a hydrophobic treatment are more preferable.

2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, etc.) , Barium sulfate, calcium carbonate, etc.).

3) Lubricants: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like.

These additives are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the toner particles.
0.1 to 5 parts by weight are used. These additives may be used alone or in combination of two or more.

In the dispersion medium used in the present invention, any suitable stabilizer can be used. For example, as inorganic compounds, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite,
Silica and alumina. As an organic compound,
Polyvinyl alcohol, gelatin, methyl cellulose,
Sodium salts of methylhydroxypropylcellulose, ethylcellulose, carboxymethylcellulose, polyacrylic acid and salts thereof, starch and the like can be used by dispersing them in an aqueous phase. It is preferable to use 0.2 to 20 parts by weight of these stabilizers based on 100 parts by weight of the polymerizable monomer.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium. For example, in the case of calcium phosphate, it is preferable to mix an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high stirring.

In order to finely disperse these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the initial action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
Examples include sodium oleate, sodium laurate, potassium stearate, calcium oleate, and the like.

The polymerized toner of the present invention can be obtained by the following method.

That is, a releasing agent, a coloring agent,
A charge controlling agent, a polymerization initiator, and other additives are added, and the monomer system uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like is mixed with an ordinary stirrer or homogenizer in an aqueous phase containing a dispersion stabilizer. Disperse with a mixer, homogenizer or the like. Preferably, the granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less. Thereafter, stirring may be performed to such an extent that the particle state is maintained and sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization temperature is 40
The polymerization is carried out at a temperature of at least 50 ° C., generally from 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers and by-products which may cause odor at the time of fixing toner, the latter half of the reaction or the end of the reaction. Later, a part of the aqueous medium may be distilled off. After completion of the reaction, the generated toner particles are collected by washing and filtration and dried. The removal of the release agent by the surface modifying liquid may be performed at any time before or after washing the dispersion stabilizer or during the filtration step. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

[0061]

The present invention will be specifically described below based on examples and comparative examples.

Example 1 To 715 g of ion-exchanged water, 455 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added, and after heating to 60 ° C., 1.0 M-C
62.8 g of an aCl ₂ aqueous solution was gradually added, and Ca ₃ (PO
₄ ) An aqueous medium containing ₂ was obtained.

Styrene 175 g n-butyl acrylate 25 g C.I. I. Pigment Blue 15: 3 12 g Styrene-methacrylic acid-methyl methacrylate (85: 5: 10) molecular weight (Mw = 58,000) 6 g Paraffin wax (mp. 70 ° C.) 60 g Di-t-butylsalicylate metal compound 3 g

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To disperse and dissolve uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile)
[T1 / 2 = 140 min. at 60 ° C.], 10 g, and dimethyl-2,2′-azobisisobutyrate [t1 /
2 = 1,270 min. at60 ° C, t1 / 2 = 80m
in. at 80 ° C.] was dissolved to prepare a polymerizable monomer system.

The above polymerizable monomer system was charged into the aqueous medium, and the mixture was stirred at 60 ° C. under a N ₂ atmosphere at 10,000 rpm for 20 minutes using a TK homomixer, and the suspension droplets having the toner particle size were removed. Granulated. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade. At this point, the polymerization conversion was 90%. Thereafter, the reflux of the steam was stopped, the liquid temperature was raised to 80 ° C., and stirring was continued for another 10 hours. After completion of the reaction, 25 parts by weight of SC CLEANER-B (manufactured by Diafloc) was added to 100 parts by weight of the dispersion medium in the suspension, mixed and stirred for 1 hour, and then cooled.
Hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , followed by filtration and drying to obtain a polymerized toner.

The surface of the obtained toner was analyzed by XPS.
% By weight, and the blocking resistance was remarkably excellent.

The BET was added to 100 parts by weight of the toner.
0.7 parts by weight of hydrophobic silica having a specific surface area of 210 m ² / g according to the method was externally added. A ferrite carrier 93 coated with an acrylic resin was added to 7 parts by weight of the external additive toner.
Parts by weight were mixed to obtain a developer.

This developer was used in a commercially available copy machine, CLC
-500 (manufactured by Canon Inc.) and subjected to a durability test on an actual machine. The fixing device used was a fluorine-based roller having no oil application function. The process speed is 100 mm / sec, and the developing condition is 30 ° C./85.
% In a high-temperature, high-humidity environment.

As a result, it was possible to obtain a good image which was excellent in fixing property and the same as the initial one even after 6,000 sheets of durability.

Example 2 172 g of styrene 28 g of n-butyl acrylate I. Pigment Blue 15: 3 10 g Styrene-methacrylic acid-methyl methacrylate (85: 5: 10) molecular weight (Mw = 58,000) 5 g Paraffin wax (mp. 60 ° C.) 50 g Di-t-butylsalicylic acid metal compound 4 g

A polymerizable composition as described above is obtained. Further, STRIPPER Q-10 (manufactured by Diafloc) is selected as the surface modification liquid, and after the polymerization reaction is completed, 6 parts by weight of the suspension is added to 100 parts by weight of the dispersion medium. Otherwise,
Polymerized toner was obtained in the same manner as in Example 1.

The content ratio of the wax in the surface component of the obtained toner was 2.3% by weight, the blocking resistance was remarkably excellent, the fixing property was excellent, and the durability under high temperature and high humidity was 50%.
Even after 00 sheets, a good image which was not different from the initial image could be obtained.

Example 3 170 g of styrene 30 g of n-butyl acrylate I. Pigment Blue 15: 3 10 g Styrene-methacrylic acid-methyl methacrylate (85: 5: 10) molecular weight (Mw = 58,000) 5 g 80 g of ester wax having the following structural formula (mp. 55 ° C.)

[0074]

Embedded image Di-t-butylsalicylic acid metal compound 4 g

A polymerizable composition as described above is obtained. OAKITE33 (manufactured by Diafloc) is selected as the surface modification liquid, and after the polymerization reaction is completed, 20 parts by weight of the suspension is added to 100 parts by weight of the dispersion medium. Other than this, Example 1
A polymerized toner was obtained with the same formulation as described above.

The content ratio of the wax in the surface component of the obtained toner was 3.9% by weight, the blocking resistance was remarkably excellent, the fixing property was excellent, and the durability under high temperature and high humidity was 40%.
Even after 00 sheets, a good image which was not different from the initial image could be obtained.

COMPARATIVE EXAMPLE 1 A polymerized toner was obtained in the same manner as in Example 1 without using the surface modifying liquid and without treating the wax.

The content ratio of wax in the surface components of the obtained toner was 5.8% by weight. Although this toner has excellent blocking resistance and fixing property, it has durability under high temperature and high humidity.
After 000 sheets, an image deteriorated from the beginning was obtained.

Comparative Example 2 172 g of styrene 28 g of n-butyl acrylate I. Pigment Blue 15: 3 10 g Styrene-methacrylic acid-methyl methacrylate (85: 5: 10) Molecular weight (Mw = 58,000) 5 g Paraffin wax (mp. 60 ° C.) 55 g Di-t-butylsalicylic acid metal compound 4 g

A polymerizable composition as described above is obtained. After the completion of the polymerization reaction, 24 parts by weight of 1-propanol, which is a water-soluble organic solvent, is added to 100 parts by weight of the dispersion medium. Except for this, a polymerized toner was obtained in the same formulation as in Example 1.

The abundance ratio of the wax in the obtained toner surface component was 5.9% by weight. Although this toner has excellent blocking resistance and fixing properties, it has a durability of 20 under high temperature and high humidity.
An image deteriorated from the beginning was obtained after 00 sheets.

Comparative Example 3 172 g of styrene 28 g of n-butyl acrylate I. Pigment Blue 15: 3 10 g Styrene-methacrylic acid-methyl methacrylate (85: 5: 10) molecular weight (Mw = 58,000) 5 g Paraffin wax (mp. 65 ° C.) 76 g Di-t-butylsalicylate metal compound 6 g

A polymerizable composition as described above is obtained. Also, SC CLEANER-B (manufactured by Diafloc) was selected as the surface modification liquid, and after the polymerization reaction was completed, the dispersion medium 1 was added to the suspension.
2 parts by weight are added to 00 parts by weight. Except for this, a polymerized toner was obtained in the same formulation as in Example 1.

The wax content in the surface components of the obtained toner was 7.0% by weight. Although this toner had good fixability, the blocking resistance and durability were extremely poor, and an image deteriorated from the initial stage was obtained on 50 sheets under high temperature and high humidity.

Comparative Example 4 In Example 1, after the completion of the reaction, the suspension was filtered without adding the surface modifying liquid to the toner, and then the toner was added to n-hexane and mixed for 1 hour. After removing the wax on the surface, the mixture was filtered and dried.

Although the obtained toner can obtain substantially the same results as in Example 1, the process becomes complicated, and the time required to obtain the toner is twice as long as that of Example 1, and the efficiency is improved. A problem occurred on the surface.

[0087]

According to the present invention, a toner for developing an electrostatic charge image having excellent blocking resistance and fixability can be obtained. In particular, the durability under high temperature and high humidity is remarkably improved, and the toner is stable and excellent over a long period of time. Images can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kasugani Rare 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Takao Ishiyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP-A-2-256069 (JP, A) JP-A-63-247759 (JP, A) JP-A-1-108555 (JP, A) (58) Fields investigated (Int. (Cl. ⁷ , DB name) G03G 9/08

Claims (3)

(57) [Claims] 1. A polymerizable monomer, a colorant and the polymerizable monomer
Suspension polymerization of a monomer composition containing at least 10 to 40 parts by weight of a release agent per 100 parts by weight of a body in an aqueous medium
Polymerization process, and after the polymerization process, surface in suspension
Step of removing the release agent on the toner surface by adding a reforming liquid
In the method for producing a polymerized toner for developing an electrostatic image , at least the ratio of the release agent in the surface component of the toner,
Is less than 5% by weight . 2. In the step of removing the release agent on the surface of the toner, any one of a surfactant, an organic acid, an organic acid salt, an aliphatic amine derivative, a water-soluble organic solvent, potassium hydroxide, phosphoric acid and pure water is used. 2. The method for producing a toner for developing an electrostatic image according to claim 1, further comprising adding a surface modification liquid obtained by combining part or all of the above. 3. An electrostatic image developing toner obtained by the production method according to claim 1.