JPH07128908A - Electrostatic charge image developing toner and its production - Google Patents

Abstract

PURPOSE:To produce an electrostatic charge image developing toner excellent in low-temp. fixability, mold releasability and blocking resistance and also enhanced in durability under high-temp. and high-humidity conditions. CONSTITUTION:A monomer composition contg. at least a polymerizable monomer, colorant and mold release agent is suspension-polymerized in aq. medium to directly produce an electrostatic charge image developing polymerized toner. The composition contains 10-40 pts.wt. of the mold release agent, based on 100 pts.wt. of the polymerizable monomer, and a surface-reforming soln. is added after polymerization to remove the mold release agent on the toner surface.

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 developing an electrostatic latent image in electrophotography and the like, and a method for producing the toner.

[0002]

BACKGROUND OF THE INVENTION Electrophotography is described in US Pat. No. 2,297,
As described in Japanese Patent Application No. 691 etc., a number of methods are known, and 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 with toner, the toner image is transferred to a transfer member such as paper, if necessary, and then fixed by heating, pressurizing, solvent vapor or the like to obtain a copy. Further, as a method of developing with 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 toners having a desired particle size by a fine pulverizer and a classifier after melt-mixing a colorant consisting of dyes and pigments in a thermoplastic resin and uniformly dispersing them. Has been manufactured.

Due to manufacturing restrictions, the toner produced by this manufacturing method is required to have good meltability when heat is applied, to have a low softening point, low melt viscosity and high sharp meltability. It

However, such a toner having a high sharp melting property has a high affinity with a fixing roller of an image forming apparatus or the like and tends to be offset to the fixing roller during fixing.

Therefore, conventionally, in order to improve the releasing property of the toner from the fixing roller, a releasing agent such as silicone oil is applied to the fixing roller. However, in such an image forming method, the following problems have occurred.

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

Furthermore, in accordance with various copying needs in recent years,
It is widely used to pass film-shaped resin, etc., but the film for overhead projectors, also known as transparency film, is generally well known. However, in such a fixing method, a sticky feeling due to oil application can be avoided. However, there remains a big problem in the quality of the obtained image. On the other hand, with the speeding up of copying machines and further energy saving, further low temperature fixability and offset resistance of toner are required.

With respect to these problems, there are great expectations for establishing a fixing system that does not require oil coating and developing a new toner for achieving the fixing system.

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

In this suspension polymerization method, since droplets of the monomer composition are formed in a dispersion medium of water, which has a large polarity,
The component having a polar group contained in the monomer composition tends to exist in the surface layer portion which is the interface with the aqueous phase, and the non-polar component does not exist in the surface layer portion, which is a so-called core / shell structure. By utilizing this characteristic of the manufacturing method, it is possible to contain a wax having a low melting point which cannot be used by other pulverization methods.

[0012] The toner obtained by the polymerization method can achieve both anti-blocking properties and low-temperature fixing properties, which are contradictory properties, by encapsulating the low melting point wax. That is, by encapsulating the low-melting-point wax, 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 is possible. More preferably,
The wax that melts during fixing also acts as a release agent,
Without applying a release agent such as oil to the fixing roller,
It is possible to prevent high temperature offset.

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

However, recently, when the outermost surface layer of the polymerized toner in which a large amount of wax is encapsulated in order to obtain a good fixing property is measured by XPS, the wax abundance ratio in the toner surface component is 5 It was found to be over weight%.

The presence of the wax on the surface of the toner pollutes the developing sleeve, the photosensitive drum, the transfer drum, etc., and becomes a factor of lowering the durability.

As a method for removing contaminants existing on the surface of the toner, the toner recovered after the polymerization is treated with an organic solvent which does not dissolve the binder resin.
Method for removing residual dispersion stabilizer and contaminants (Japanese Patent Laid-Open No. 2-2
45768) or a water-soluble organic solvent that does not dissolve the binder resin, and a method for removing the residual dispersion stabilizer (JP-A-2-
64652). However, these methods have a problem that the removing step is complicated, and the wax cannot be removed even if the step is easy.

[0017]

The present inventors have heretofore considered that in suspension polymerization in an aqueous medium, the polar component is concentrated near the interface and the nonpolar component is collected in the center, and We have developed a polymerized toner that contains a large amount of wax components that cannot be manufactured by a toner manufacturing method that relies on kneading and crushing, and has developed a toner that can be fixed at low temperatures and does not require the application of a release agent to the fixing device during fixing. Obtained.

However, when a large amount of low-temperature melting wax is contained in this polymerized toner system, a high quality image can be obtained without any problem under normal environment, but with an increase in the number of durable sheets, the sleeve and drum Due to the cause of pollution, etc., the phenomenon that the durability under high temperature and high humidity was significantly reduced occurred.

An object of the present invention is to provide an electrostatic charge image developing toner which solves the above problems.

Another object of the present invention is to provide a toner for developing an electrostatic charge image, which is fixed at a low temperature, is excellent in releasing property and is excellent in blocking resistance.

A further object of the present invention is to provide a method capable of producing the above-mentioned toner for developing an electrostatic image by removing contaminants on the toner surface by a simple method.

[0022]

MEANS TO SOLVE THE PROBLEMS [Means and Actions for Solving the Problems] The present invention, which was conceived to achieve the above object, provides a monomer composition containing at least a polymerizable monomer, a colorant and a release agent in an aqueous medium. In a method for producing a polymerized toner for electrostatic image development, which is directly obtained by suspension polymerization, the release agent is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of a polymerizable monomer, and the toner after the polymerization step is completed. A method for producing a toner for developing an electrostatic charge image, which comprises a step of removing a release agent on the surface, and a toner for developing an electrostatic charge image obtained by this production method.

The present invention will be specifically described below.

As a result of earnest studies on the method for producing a polymerized toner, the present inventors have found that by removing the release agent on the surface of the toner after the polymerization step, the durability can be remarkably improved mainly at high temperature and high humidity. DISCLOSURE OF THE INVENTION 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 carried out by adding the surface modification liquid after the completion of the polymerization step. As a specific example of this surface modification liquid,
SC CLEANER manufactured by Diafrock Co., Ltd.
7, SC CLEANER-B, SC CLEANER
-D, STRIPPER-Q / O, OAKITE-33
Etc.

Specific examples of each component of the surface modification liquid are shown below, but the components are not limited to these.

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

As the water-soluble organic solvent, alcohols such as methanol, ethanol, propanol, butanol, isobutanol, tert-butanol, hexanol and octanol, dioxane, dimethyl ether,
Ethers such as diethyl ether, tetrahydrofuran, ethylene glycol, monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and 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 derivative include an aliphatic primary amine such as methylamine, ethylamine and propylamine, an aliphatic secondary amine such as dimethylamine, diethylamine and dipropylamine, and an aliphatic tertiary amine such as trimethylamine and triethylamine. Aliphatic unsaturated amines such as amine, allylamine, diallylamine and triallylamine and their derivatives are used.

As the surface active agent, an anionic surface active agent, a cationic surface active agent, an amphoteric surface active agent and a nonionic surface active agent which are mainly water-soluble surface active agents are used. Further, any oil-soluble surfactant may be used as long as it is soluble in water.

In the present invention, the use temperature of this surface modification liquid is not particularly limited, but is preferably 60.
~ 80 ° C is desired. Further, the timing of adding the surface modifying 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 and the like.

The surface treatment time after addition is not particularly limited.

The inventors of the present invention have shown that the presence ratio of the release agent in the toner surface component can be made less than 5% by weight by adding the above-mentioned surface modification liquid after the completion of the polymerization step, by XPS (X-ray photoelectron spectroscopy). Method) to analyze the toner surface. Therefore, when the toner of the present invention is used in a copying machine or the like, the durability is improved particularly under high temperature and high humidity, and a stable and good image can be obtained for a long period of time. Regarding the durability, if the existing ratio of the release agent is less than 2.0% by weight, a remarkable effect is obtained.

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

(Apparatus) ESCALAB5 manufactured by VG (measurement condition)

[0036]

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

In the present invention, the content of the releasing agent is 10 to 40 parts by weight, more preferably 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, when 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.
It is 100 ° C. If the melting point is lower than 30 ° C., the blocking resistance and shape retention of the toner are insufficient, and 1
When it is higher than 50 ° C, the effect of 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 modified products thereof, for example, oxides and graft-treated products, higher fatty acids, and their metal salts, amide waxes, ester waxes, for example, tertiary and / or quaternary carbon A polyfunctional polyester compound obtained from a bifunctional or higher alcohol compound or a carboxylic acid compound, having a primary or / and secondary carbon, and obtained from a bifunctional or higher alcohol compound or carboxylic acid compound Examples thereof include polyester compounds and monofunctional ester compounds having tertiary or / and quaternary carbon.

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

In the present invention, it is more preferable to add a polymer / copolymer having a polar group as an additive to the monomer system for polymerization. Since the polar polymer / copolymer gathers on the surface layer of the toner particles, it forms a kind of shell-like form and imparts excellent properties such as blocking resistance to the toner particles, while By polymerizing so as to contribute to the improvement of the fixing property with a relatively low molecular weight, a toner satisfying the contradictory requirements of the fixing property and the blocking resistance can be obtained. The polar polymers / 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, nitrile monomers such as acrylonitrile, vinyl chloride, etc. 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 resin etc. are mentioned. In particular, it is preferable to add a polyester resin in terms of maintaining core / shell formation. The addition amount of these polar polymers / copolymers 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, and examples thereof include carbon black and 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. Mordant 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. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. Dyes such as Basic Green 6, yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa 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, Alkali Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Malachite Green. There are pigments such as lake and final yellow green G.
In the present invention, since the toner is obtained by using the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant. It is better to apply chemical treatment. In particular,
Many dyes and carbon black have a polymerization inhibitory property, so care must be taken when using them. A preferred method for surface-treating a dye system is a method of polymerizing a polymerizable monomer 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 in the same manner as the dye, or may be treated with a substance that reacts with the surface functional groups of the carbon black, such as polyorganosiloxane.

In the case of a color toner, 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 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, and compounds such as magnetite and ferrite. In particular, in the present invention, since a toner is obtained by using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the magnetic material, and preferably surface modification, for example, there is no polymerization inhibitory property. It is better to give a hydrophobic treatment with a substance.

In the present invention, it is desirable to add a charge control agent to the toner material for the purpose of controlling the chargeability of the toner. As these charge control agents, among known ones, those having almost no polymerization inhibitory property / water phase transfer property are used. For example, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidines are used. Derivatives, imidazole derivatives, amine-based and polyamine-based compounds, and the like. As a negative charge control agent, metal-containing salicylic acid-based compounds, metal-containing monoazo-based dye compounds, urea derivatives, styrene-acrylic acid copolymers, styrene-methacryl Examples thereof include acid copolymers. The addition amount of these charge control agents is preferably 0.1 to 10 parts by weight with respect to 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, 1'-azobis (cyclohexane-1-
Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobis or diazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
Examples thereof include peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-zochlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are polymerizable monomers 10
The amount added 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, in order to control the molecular weight, known crosslinking agents and chain transfer agents may be added, and the preferable addition amount is 0. 0 with respect to 100 parts by weight of the polymerizable monomer. 001 to 15 parts by weight.

The additive used for imparting various toner characteristics used in the present invention is not more than ⅕ of the volume average diameter of toner particles from the viewpoint of durability in the toner or when added to the toner. The particle size is preferable. The particle size of the additive means the average particle size thereof obtained by observing the surface of the toner particles with an electron microscope. As the additives for imparting these characteristics, for example, the following ones are used.

1) Flowability-imparting agent: metal oxide (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, fluorinated carbon, 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.) etc.

3) Lubricants: Fluorine-based resin powders (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), etc.

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

These additives are used in an amount of 0.1 to 10 parts by weight, preferably 100 parts by weight of the toner particles.
0.1-5 parts by weight are used. These additives may be used alone or in combination.

Any suitable stabilizer can be used in the dispersion medium used in the present invention. 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, etc.
Examples thereof include silica and alumina. As an organic compound,
Polyvinyl alcohol, gelatin, methyl cellulose,
Methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like can be used by dispersing in an aqueous phase. It is preferable to use 0.2 to 20 parts by weight of these stabilizers with respect to 100 parts by weight of the polymerizable monomer.

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

In order to finely disperse these stabilizers, 0.001 to 0.1 part by weight of a surfactant may be used. This is for promoting the initial action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, and sodium octyl sulfate.
Examples thereof 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 / coloring agent /
A monomer system in which a charge control agent, a polymerization initiator, and other additives are added and uniformly dissolved or dispersed by a homogenizer or an ultrasonic disperser is added to an ordinary stirrer or homogenizer in an aqueous phase containing a dispersion stabilizer. Disperse with a mixer / homogenizer. Granulation is preferably carried out by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally 30 μm or less. After that, the action of the dispersion stabilizer may be followed by stirring to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 40
Polymerization is carried out at a temperature of not lower than 0 ° C, generally 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 that may cause odor during toner fixing, the latter half of the reaction or the end of the reaction. After that, the aqueous medium may be partially distilled off. After the reaction is completed, the produced toner particles are collected by washing and filtration and dried. The release agent may be removed by the surface modification liquid before or after the dispersion stabilizer is washed and at any time 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]

EXAMPLES 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 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 aCl ₂ aqueous solution was gradually added to 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-butylsalicylic acid metal compound 3 g

The above formulation was heated to 60 ° C. and 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo).
Was evenly dispersed and dissolved. In addition to this, the 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. at 60 ° C, t1 / 2 = 80m
in. at 80 ° C.] 1 g was dissolved to prepare a polymerizable monomer system.

The above polymerizable monomer system was put into the above aqueous medium, and the mixture was stirred at 60 ° C. under N ₂ atmosphere with a TK type homomixer at 10,000 rpm for 20 minutes to form suspension droplets of toner particle size. Granulated. Then, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade. The polymerization conversion rate at this point was 90%. Then, the reflux of water vapor was stopped, the liquid temperature was raised to 80 ° C., and stirring was continued for 10 hours. After the reaction was completed, 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, and the mixture was stirred for 1 hour and then cooled,
Hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and the polymerized toner was obtained by filtering and drying.

An XPS analysis of the obtained toner surface revealed that the abundance ratio of wax in the toner surface component was 1.5.
%, And the blocking resistance was remarkably excellent.

BET is added to 100 parts by weight of this toner.
0.7 part 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 externally added toner.
Part by weight was mixed to obtain a developer.

This developer was applied to a commercially available copier, CLC.
It was put into a modified machine of -500 (manufactured by Canon Inc.) and a durability test was conducted on an actual machine. As the fixing device, a fluorine type roller having no oil application function was used. The process speed is 100 mm / sec and the developing condition is 30 ° C / 85.
% High temperature and high humidity environment.

As a result, it was possible to obtain a good image which was excellent in fixing property and which was the same as the initial image even after 6000 sheets of durability.

Example 2 Styrene 172 g n-Butyl acrylate 28 g C.I. 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 such as the above is obtained. Further, STRIPPER Q-10 (manufactured by Diafloc Co., Ltd.) is selected as the surface modification liquid, and 6 parts by weight is added to 100 parts by weight of the dispersion medium in the suspension after the completion of the polymerization reaction. Other than this,
A polymerized toner was obtained with the same formulation as in Example 1.

The abundance ratio of wax in the surface component of the obtained toner was 2.3% by weight, the blocking resistance was extremely excellent, the fixing property was also excellent, and the durability under high temperature and high humidity was 50.
Even after 00 sheets, good images that were the same as those at the beginning could be obtained.

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

[0074]

[Chemical 1] Di-t-butylsalicylic acid metal compound 4 g

A polymerizable composition such as the above is obtained. Further, AKITE 33 (manufactured by Diafloc Co., Ltd.) is selected as the surface modification liquid, and 20 parts by weight of the dispersion medium is added to 100 parts by weight of the dispersion medium after the completion of the polymerization reaction. Other than this, Example 1
A polymerized toner was obtained with the same formulation.

The abundance 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, good images that were the same as those at the beginning could be obtained.

Comparative Example 1 A polymerized toner was obtained in the same manner as in Example 1, except that the surface modification liquid was not used and the wax was not treated.

The abundance ratio of wax in the surface component of the obtained toner was 5.8% by weight. Although this toner has excellent blocking resistance and fixability, it has a high durability under high temperature and high humidity.
After 000 sheets, an image deteriorated from the initial stage was obtained.

Comparative Example 2 Styrene 172 g n-Butyl acrylate 28 g C.I. 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 such as the 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 in the suspension. Except for this, a polymerized toner was obtained in the same formulation as in Example 1.

The abundance ratio of wax in the obtained toner surface component was 5.9% by weight. Although this toner has excellent blocking resistance and fixability, it has a durability of 20 at high temperature and high humidity.
After 00 sheets, an image deteriorated from the initial stage was obtained.

Comparative Example 3 Styrene 172 g n-Butyl acrylate 28 g C.I. 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-butylsalicylic acid metal compound 6 g

A polymerizable composition such as the 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.
Add 2 parts by weight to 00 parts by weight. Except for this, a polymerized toner was obtained in the same formulation as in Example 1.

The abundance ratio of wax in the surface component of the obtained toner was 7.0% by weight. Although this toner has good fixability, its blocking resistance and durability are extremely poor, and an image deteriorated from the initial stage was obtained after 50 sheets under high temperature and high humidity.

Comparative Example 4 In Example 1, after the reaction was completed, the toner was filtered without adding the surface modification liquid into the suspension, and then the toner was added into n-hexane and mixed for 1 hour to obtain the toner. After removing the wax on the surface, it was filtered and dried.

Although the toner obtained has almost the same results as in Example 1, the process is complicated and the time required to obtain the toner is twice as long as that in Example 1, resulting in higher efficiency. There was a problem in terms of surface.

[0087]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Rare Kasuya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takao Ishiyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Within the corporation

Claims (3)

[Claims] 1. A method for producing a polymerized toner for electrostatic image development, which is directly obtained by suspension polymerization of a monomer composition containing at least a polymerizable monomer, a colorant and a release agent in an aqueous medium. In the above, the release agent is added in an amount of 10 to 4 with respect to 100 parts by weight of the polymerizable monomer.
A method for producing a toner for developing an electrostatic charge image, which comprises 0 part by weight and comprises a step of removing a releasing agent on the surface of the toner after the polymerization step. 2. In the step of removing the releasing agent on the surface of the toner, among the surfactant, the organic acid, the organic acid salt, the aliphatic amine derivative, the water-soluble organic solvent, potassium hydroxide, phosphoric acid and pure water. The method for producing a toner for developing an electrostatic charge image according to claim 1, characterized in that a surface modification liquid obtained by combining a part or all of the above is added. 3. An electrostatic image developing toner obtained by the manufacturing method according to claim 1.