JPS63198075A - Production of polymerized toner - Google Patents

Abstract

PURPOSE:To obtain a polymer toner sharp in particle size distribution and good in developability characteristics at a good yield by using a hardly water-soluble inorganic fine powder in a dispersion medium and a polar substance in a monomer composition, and setting a specified surface tension between the composition and the dispersion medium. CONSTITUTION:The monomer composition containing the polymerizable monomer, the polar substance, and a colorant is polymerized in the dispersion medium containing the inorganic dispersant powder soluble in Bronsted acid and hardly soluble in water, and substantially no water-soluble surfactant, and having a pH of 2.5-6.0, or 7.1-11.0, and in this case, expression 1 shown on the right is satisfied, where A is the surface tension between the monomer composition except the colorant and the dispersion medium, and B is that between the monomer composition except the colorant, and the ion-exchanged water, and a hardly water-soluble polar substance high in hydrophobicness can be used as the polar substance, thus permitting a toner sharp in the particle size distribution and consequently, superior in developability characteristics to be formed.

Description

[Detailed description of the invention] 1! TECHNICAL FIELD The present invention relates to a method for producing a toner used in a method for visualizing a latent image.

IL-I Toner that visualizes electrical and magnetic latent images is used in various processes for forming and recording images.

As one of such image forming processes, electrophotography, many methods are known, such as those described in US Pat. No. 2,297.69. This electrophotographic method generally uses a photoconductive substance to form an electrical latent image on a photoreceptor by various means, and then develops the latent image with toner to form a toner image. Then, if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed to the transfer material using heat, pressure, solvent vapor, etc., thereby obtaining a copy. Furthermore, various methods have been proposed as methods for developing with toner or methods for fixing toner images, and methods suitable for each image forming process are adopted.

Conventionally, toners used for these purposes are generally prepared by melting and mixing a colorant made of a magnetic material or dye/pigment in a thermoplastic resin, uniformly dispersing the colorant, and then finely pulverizing the colorant.
By classifying toners, toners having a desired particle size have been manufactured.

According to this production method (pulverization method), a fairly good toner can be produced, but there are certain limitations, namely the range of selection of toner materials.For example, the resin colorant dispersion is sufficiently brittle, Due to this requirement, the resin colorant dispersion must be made sufficiently brittle that it must be able to be finely pulverized using economically available production equipment, so the dispersion must actually be pulverized at high speed. When doing so, a problem arises in that a particle group with a wide particle size range is likely to be formed, and in particular, a relatively large proportion of excessively finely ground particles are included in this particle group. Furthermore, such a highly brittle material is susceptible to further pulverization or powdering when actually used for development in a copying machine or the like.

In addition, in this pulverization method, it is difficult to completely and uniformly disperse solid particles such as magnetic powder or colorant into the resin, and depending on the degree of dispersion of these fixed particles, fog may increase and image density may decrease. Careful attention must be paid to the extent of this dispersion, as it causes a decrease in
Exposure of the colorant to the fractured surface of the colored resin fine powder may cause variations in toner development characteristics.

On the other hand, in order to overcome the problems of toner produced by these pulverization methods, a method for producing toner using a suspension polymerization method has been proposed. In this suspension polymerization method, a monomer in which a polymerizable monomer and a coloring agent (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) are uniformly dissolved or dispersed is used. The composition is introduced into an aqueous phase (ie, continuous phase) containing a suspension stabilizer, and is granulated and polymerized with stirring to form toner particles.

This suspension polymerization method is a preferred toner manufacturing method because it does not include any pulverization process, does not require the toner material to be brittle, and does not expose the colorant to the toner fracture surface. The toner is spherical in shape and has various advantages such as excellent fluidity and uniform triboelectric charging properties. However, in this suspension polymerization, it is necessary to carry out the polymerization in a stable suspension system where the monomer composition particles do not coalesce, or to form fine polymer particles with a uniform particle size distribution by polymerization. Obtaining this is not always technically easy.

Not only toners obtained by this suspension polymerization method, but also toners used in methods for visualizing latent images, are required to control various properties in order to faithfully reproduce the original. Among the characteristics of particles, control of particle size distribution is one of the most important issues. In other words, when an image is formed using a toner that has a broad particle size distribution and contains a large amount of particles with a non-standard particle size, the sharpness of the image may be affected due to toner scattering, fogging, unevenness, etc. In addition, problems such as deterioration of toner durability arise due to variations in toner development characteristics.

Conventionally, in this suspension polymerization method, various methods have been proposed in order to sharpen the particle size distribution of the toner. A method of adjusting the particle size by a combination of methods, a method of adjusting the particle size by adding an aqueous phase polymerization inhibitor as disclosed in JP-A No. 56-156839, etc. have been proposed, but a polymerized toner having a preferable particle size distribution has not yet been obtained. Not yet.

In particular, surfactants such as anionic surfactants are difficult to remove even by washing with water, and therefore tend to remain on the surface of toner particles, which has the drawback of easily causing a deterioration of toner development characteristics.

Due to the above-mentioned problems, there is a strong desire for a dispersant that sharpens the toner particle size distribution and has less influence on development characteristics.

11 Standing Beans 1 An object of the present invention is to provide a method for producing toner that solves the above-mentioned problems.

Another object of the present invention is to provide a method for producing a polymerized toner having a sharp particle size distribution with a high yield.

Still another object of the present invention is to provide a method for producing a polymerized toner with good development characteristics.

As a result of intensive research, the present inventors have found that the combination of a polar substance contained in a monomer composition and a specific poorly water-soluble inorganic dispersant powder can suitably adjust the interfacial tension. make it possible,
Furthermore, it has been found that coalescence of toner particles can be effectively suppressed to provide a polymerized toner having a sharp particle size distribution and excellent development characteristics.

The method for producing a polymerized toner of the present invention is based on the above findings, and more specifically, it contains a poorly water-soluble inorganic dispersant powder soluble in Brønsted acid, and p)1 is 2.5 to 6.
The polymerizable monomer, the polar substance, and the colorant are mixed at least in a dispersion medium that is in the range of 0 or 7.1 to 1"1.0 and does not substantially contain a water-soluble surfactant. A method of polymerizing a monomer composition comprising: The interfacial tension (A) between the monomer composition excluding the colorant and the dispersion medium is (in the above formula, B is The method is characterized in that the relationship between ), which represents the interfacial tension between the monomer composition excluding the colorant and ion-exchanged water, is calculated.

The functions of the toner manufacturing method of the present invention having the above configuration will be described below in comparison with the conventional method.

That is, in the suspension polymerization method, generally, a polymerizable monomer system that is substantially incompatible with a dispersion medium typified by water is dispersed and polymerized to form toner particles.
In order to obtain polymerized toner particles with a sharp particle size distribution,
An extremely important issue is how to stably maintain the droplets of the polymerizable monomer system (monomer composition particles) suspended in the liquid dispersion medium at a constant diameter during the polymerization process.

Conventionally, as a means to solve such problems, generally,
It has been attempted to lower the monomer composition (oil droplets)-dispersion medium interfacial tension by adding water-soluble surfactants to the dispersion medium.

However, when such a water-soluble surfactant is added, the formation of emulsion particles (particle size of 1μ or less) due to partial emulsification of the monomer composition is unavoidable. Since it had a strong tendency to remain on the toner surface, the particle size distribution of the toner became broad, making it difficult to obtain a toner with good development characteristics.

On the other hand, when the above-mentioned water-soluble surfactant is not used, there is a strong tendency for coarse monomer composition particles to be formed due to insufficient reduction in interfacial tension, and coarse toner particles are generated.
The toner particle size distribution also tended to be broad.

On the other hand, in the production method of the present invention, the polar substance contained in the monomer composition and the inorganic dispersant soluble in Brønsted acid interact without using a water-soluble surfactant. This action achieves a suitable interfacial tension between the monomer composition particles (droplets) and the dispersion medium. Therefore, according to the present invention, monomer composition particles having a fine particle size and a sharp particle size distribution substantially free of emulsion particles can be obtained. Furthermore, in the present invention, based on the interaction with the polar substance described above, the poorly water-soluble inorganic dispersant powder more firmly holds the monomer droplets and prevents the coalescence of the droplets during the polymerization process. The particle size distribution is sharp and (by not using conventional surfactants)
A polymerized toner with excellent development properties can be obtained.

Furthermore, according to the method of the present invention, it is possible to use a highly hydrophobic and poorly water-soluble polar substance (which was difficult to use in conventional methods) as the polar substance, resulting in a sharp particle size distribution and improved development characteristics. It becomes possible to form a toner with even better (especially environmental characteristics).

The present invention will be explained in more detail below. In the following description, "1 part" and "1%" expressed in quantitative terms are based on weight unless otherwise specified.

In the production method of the present invention, the monomer composition containing at least a polymerizable monomer, a polar substance, and a colorant has an interfacial tension with this monomer composition within a specific range. Polymerized in a dispersion medium.

If the interfacial tension is (A) and the interfacial tension between the model composition and ion-exchanged water is (B), then in the present invention, it is necessary that the following is true, and it is preferable that the following is true.

When this value is less than 5, the reduction in interfacial tension obtained by the polar substance is small, and the reduction in interfacial tension is inhibited, resulting in the formation of an emulsion of the monomer composition, which is not desirable. The interfacial tension becomes relatively high, resulting in poor granulation properties.

In the present invention, a composition (model composition) obtained by removing the colorant (pigment, magnetic particles, etc.) from the monomer composition is used to measure the interfacial tensions (A) and (B).

According to the findings of the present inventors, even if such a model composition is used, measurement errors due to interfacial tension values (due to increased viscosity, etc.) that are virtually unchanged from those when the monomer composition itself is used. ) is preferable because it can eliminate such a model composition. Therefore, in the present invention, such a model composition is used for convenience in carrying out interfacial tension measurement.

This "model composition" needs to contain at least a polymerizable monomer and a polar substance, but if necessary, among the various additives described below that are added to the monomer composition (interfacial tension It is preferable to contain a charge control agent and/or a crosslinking agent (additives that do not adversely affect the measurement). Among the additives described below, low softening point compounds (paraffin etc.) ), it is preferable not to include it in the model composition because it may cause errors in interfacial tension measurements.

In the present invention, the preferable range of the interfacial tension (A) is 1
8 to 2 dyne/cm, and the interfacial tension ([1)
The preferred range is 22 to 3 dyne/c+*.

In the present invention, the interfacial tension (A) and CB) are measured using a surface tension measuring device (KYOWA CBVP 5urface Ten5i manufactured by Kyowa Kagaku Co., Ltd.).
on Meter^3) at room temperature (20-30℃)
Use the value measured by a conventional method.

An outline of this interfacial tension measurement method is described below.

(1) Pour the dispersion medium (or ion-exchanged water) into a container that has been cleaned using a conventional method, and then
(mx24mm) completely immersed.

(2) Next, the polymerizable monomer composition (model composition) is gently poured into the container and allowed to stand at room temperature for 30 minutes.

(3) Next, gently pull up the glass detection plate and measure the interfacial tension.

In the present invention, as the polar substance contained in the monomer, a substance having a polar group in the molecule and causing a decrease in interfacial tension at the interface between water and the polymerizable monomer system is used.

Further, the polar substance used in the present invention is preferably a poorly water-soluble substance from the viewpoint of improving the environmental characteristics of polymerized toner particles.

Here, the term "poorly water-soluble substance" refers to a substance having a solubility of 1 g or less in 100 mA of water, preferably 500 mg or less, particularly preferably 100+ag or less.

In the present invention, both low-molecular compounds and high-molecular compounds are used as such polar substances, but in the case of high-molecular compounds, the ffl weight average molecular weight measured by GPC (gel permeation chromatography) is s, o
oo to 500,000 is preferably used because it dissolves and disperses well in the polymerizable monomer and also imparts durability to the toner.

More specifically, anionic or cationic compounds as shown below are preferably used as this polar substance.

(1) Anionic compounds, including anionic polar groups such as carboxyl groups, hydroxyl groups, dibasic acid groups, dibasic acid anhydride groups, sulfonic acid groups, sulfonate groups, phosphate ester groups, and ether bonds. Compounds; More specifically, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated dibasic acids, anhydrides of unsaturated dibasic acids, acrylic esters and methacrylic esters having a hydroxyl group, etc. Polymers or copolymers of polar vinyl monomers; or copolymers of these polar vinyl monomers with styrene, acrylic esters, and methacrylic esters: polyester resins; cyclized rubber; chromium complexes of alkyl-substituted salicylic acids: Isopropyl triisostearoyl titanate, Isopropyl tridecylbenzenesulfonyl titanate, Isopro and Lutris (dioctyl pyrophosphate)
Titanate, Bis(dioctyl pyrophosphate) oxyacetate titanate, Bis(dioctyl pyrophosphate) ethylene titanate, Isobrobyl trioctaine titanate, Isopropyl dimethacrylylisostearoyl titanate, Isopropyl tri(dioctyl phosphate) titanate, Isopropyl tricumylphenyl titanate, Di Examples include titanate coupling agents such as milphenyloxyacetate titanate and diisostearoyl ethylene titanate.

(2) Cationic compound For example, a nitrogen-containing compound containing a basic polar group such as a -class amino group, a secondary amino group, or a tertiary amino group; specifically, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, etc. A polymer or copolymer of a nitrogen-containing monomer, a copolymer of styrene and the nitrogen-containing monomer, or styrene, an unsaturated carboxylic acid ester (for example, an acrylic ester, a methacrylic ester), etc. Copolymer with the nitrogen-containing monomer: isopropyl tri(N-aminoethyl-aminoethyl)
Examples include amino group-containing titanate coupling agents such as titanates.

Here, when the polar substance is an anionic polar polymer, it is preferable that the acid value and/or hydroxyl value is 0.5 to 100, and the amount added to 100 parts of the polymerizable monomer is 0. .1 to 50 parts is preferred.

Further, when the polar substance is a cationic polar polymer, it is preferable that the amine value is O15 to 100, and
The amount added to 100 parts of the polymerizable monomer is 0.1 to 5
Preferably it is 0 parts.

If the acid value and/or hydroxyl value or amine value of the polar polymer used in the present invention is less than 0.5, the effect of lowering the interfacial tension will be small; on the other hand, if these values exceed 100,
It is undesirable because it is too hydrophilic.

Here, the acid value refers to the number of mg of potassium hydroxide required to neutralize carboxyl groups contained in 1 g of sample.

The hydroxyl value refers to the B number of potassium hydroxide required to neutralize acetic acid bonded to hydroxyl groups when 1 g of a sample is acetylated by a specified method.

Moreover, the amine value refers to the B number of potassium hydroxide required to neutralize the hydrochloric acid required to neutralize 1 g of the sample.

As mentioned above, a polar substance having surface activity that dissolves and disperses in the polymerizable monomer is added to the monomer composition as an additive.
For example, a preferred polymerized toner can be obtained by adding a polar polymer, a polar copolymer, a cyclized rubber, or a polyester to polymerize the polymerizable monomer. These polar polymers, polar copolymers or cyclized rubbers contain 100% of the polymerizable monomer
1! 0.1 to 50 parts by weight, preferably 1 to 50 parts by weight
It is preferable to add 4011 parts by weight; if it is less than 0.1 part by weight, it is difficult to obtain a sufficient quasi-capsule structure;
If the amount exceeds 1 part by weight, the amount of polymerizable monomer becomes insufficient and the properties as a polymerized toner tend to deteriorate. It is preferable to suspend the polymerizable monomer composition containing the above in an aqueous phase of an aqueous medium in which a fine powder dispersion stabilizer is dispersed, and to polymerize the polymerizable monomer composition.

In this case, the added polar polymer, polar copolymer, cyclized rubber, or polyester gathers on the surface layer of the toner particles, forming a hammer shell-like shape, and the resulting particles become pseudo-capsules. It comes to have a structure. The relatively high molecular weight polar polymer, polar copolymer, or cyclized rubber that gathers on the surface layer of the particles gives the toner anti-blocking properties.
Provides excellent properties such as developability, charge controllability, and abrasion resistance.

On the other hand, the poorly water-soluble inorganic dispersant that is soluble in Bronsted acid and used in the present invention is a poorly water-soluble inorganic compound that is soluble in Bronsted acid (more specifically, in 100 mfL of water). 20g or more).

Here, the poorly water-soluble inorganic compound is 100 sJ of neutral ion-exchanged water! 10mg or less (preferably 5B
(below).

Examples of poorly water-soluble inorganic dispersants used in the present invention are shown below.

(1) Inorganic compounds that are neutral or alkaline in water, such as calcium phosphate, magnesium phosphate,
Calcium sulfate, magnesium carbonate, calcium carbonate, Ca3 (PO4)* *Ca (OH) 2, etc.

(2) Inorganic compounds exhibiting acidity in water, such as inorganic compounds consisting of amphoteric elements (elements that produce amphoteric oxides) such as aluminum phosphate, zinc phosphate, and zinc carbonate.

The particle size of such an inorganic compound is preferably 2 μm or less, more preferably 1 μm or less in terms of primary particles.

The particle size of the poorly water-soluble inorganic dispersant mentioned above in the dispersion medium is
Measured by Coulter Counter.

That is, a sample (inorganic compound) was added to a 1% saline solution to a concentration of approximately 10%, and after ultrasonic dispersion (36 KHz, 100 W, 1 minute) by a conventional method, 100μ
■Measure with a Coulter counter using an orifice in the usual manner.

In the number distribution of inorganic dispersants measured by this method, the proportion of particles with a particle size of 5.04 μm or more is 5.
% or less, and it is more preferable that the proportion of particles having a particle size of 3.17 μm or more is 5% or less in number.

Further, in the present invention, the volume average particle size of the inorganic dispersant in the dispersion medium is preferably 1 to 5 μ■. Means the particle size corresponding to the 50% value.

In the present invention, the above-mentioned volume average particle diameter of 1 to 5 μm is considered to indicate that the inorganic dispersant fine powder is in an association state where it is aggregated with a loose restraining force.
The fine powders are uniformly dispersed in the dispersion medium in an associative state in which the fine powders are aggregated with loose restraint rather than individually and separately (non-agglomerated state), and are further dispersed in droplets (JIL polymer composition). It is thought that the droplets are stabilized by uniformly adsorbing on the surface of the particles. As a result, in the present invention, even when the viscosity of droplets containing a polymerizable monomer system changes due to polymerization, etc., and the stability of the droplets decreases, unstable phenomena such as droplet coalescence can be prevented. It is presumed that a polymerized toner with a sharp particle size distribution that is less likely to occur can be obtained.

These inorganic dispersants may be used as they are in the form of powdered inorganic compounds, but a method in which H-soluble inorganic compounds are generated in water using substances such as sodium phosphate and calcinium chloride and then used as is is in the form of fine particles. This is preferred because an inorganic compound with good dispersibility can be easily obtained.

In general, the agglomeration that occurs in powdered poorly soluble inorganic compounds is generally a strong aggregation/state, and the particle size that leads to this agglomeration state is also uneven, so when such powder is used, it is difficult to disperse it in water. However, if the above-mentioned method of generating poorly soluble inorganic compounds in water is used, there is no need to worry about this, and a good dispersion state of the inorganic compounds can be easily obtained. It will be done.

Furthermore, when producing water-repellent compounds in water, the water-soluble neutral salts obtained together with the poorly soluble compounds have the effect of preventing the dissolution of water into water and the effect of increasing the specific gravity of water. It has both.

Examples of reactions that produce poorly soluble inorganic compounds are shown below, but the reaction is not limited thereto.

2 Na 3P O4+ 3 Ca Cj! x
-Ca a(PO4)z +6NaCfL 2 Na s PO4+ 3 M g SO4
” M g 5(PO4)2 +3Nat 5O4 2Nas Po4+Aft2 (s04)3-2Aj
! PO4+3Na, So.

Na 2 SO4+ Ca CfL2- Ca
SO4+2NaCj! Na 2 CO3+ M g SO4-M g C
Os +Na, 504 Na 2 CO3+ Ca CItz -Ca CO
3+2NaCj! 2Na, PO4+3ZnSO4mZn5(PO4)2
+3Na* 5O4 N a 2 CO2+ Z n Cj! 2- Zn
COs +2NaCj! N a 2 CO3 + Z n S Oa = Z n
CO3+Na2 So4 In the present invention, the pH of the dispersion medium containing the above-mentioned poorly water-soluble inorganic dispersant is set to 2.5-6°0, or 7.0°.
1 to 11.0.

When the pH is <2.5 or >11.0, the acidity or alkalinity of the dispersion medium becomes too strong, resulting in insufficient granulation of the monomer composition.

On the other hand, when the pH of the dispersion medium is 6.1<pH<7.1, the interfacial tension between the monomer and the surface of the composition is insufficiently lowered.

In addition, when adjusting 9N in this way, a water-soluble inorganic salt exhibiting alkalinity, a water-soluble inorganic salt exhibiting alkalinity,
Alternatively, it is preferable to adjust the pH by adding a water-soluble inorganic salt exhibiting acidity to create a dispersion medium that promotes the surface activity of polar substances.

Examples of water-soluble inorganic salts exhibiting alkalinity used in such cases include Nas po4 and Na.

CO3, NaOH%KOI (etc.).

In addition, as a water-soluble inorganic salt exhibiting acidity, MgSO
a, Ca CJ! m, Zn
S Oa % A fL K (304)
* s Aj! t (304) s s
There are ZnCf12 and the like.

In this method, two or more types of water-soluble inorganic salts may be used in combination, if necessary.

In the above, polar substances (surface-active substances) and poorly water-soluble inorganic dispersants have been explained. Preferred combinations of these are illustrated below, but the invention is not limited to these exemplified combinations.

(A) A combination of an anionic compound (1) and a poorly water-soluble inorganic dispersant (1) that is neutral or alkaline in water; (B) A combination of a cationic compound (2) and a poorly water-soluble inorganic dispersant that is acidic in water. Combination with inorganic dispersant (2).

In the above combination (A), it is more preferable to add a water-soluble inorganic salt exhibiting alkalinity to adjust the pH.

Further, in the above combination (B), it is more preferable to add a water-soluble inorganic salt exhibiting acidity to adjust the pH.

In addition, in the present invention, ZnC0, among the inorganic compounds that exhibit acidity in water, can be used in combination with an anitonic compound by adjusting the pH by adding a water-soluble inorganic salt that exhibits alkalinity. be.

Furthermore, in the above-described method, two or more poorly water-soluble inorganic dispersants may be used in combination, if necessary.

In the present invention, a dispersion medium that is substantially incompatible with the polymerizable monomer is used, and it is preferable to use an aqueous dispersion medium.

In the present invention, as the dispersion medium containing the poorly water-soluble inorganic dispersant, one that does not substantially contain a commonly known water-soluble surfactant is used. In the present invention, the water-soluble surfactant is For 100 parts of inorganic dispersant powder, o,
Although it is possible to use the water-soluble surfactant in an amount of 11 L parts or less, there is no problem even if no water-soluble surfactant is used at all.

In the present invention, when the monomer composition is granulated in an aqueous dispersion medium, it is granulated using, for example, a homomixer or homogenizer having a turbine and a stator that rotate at high speed. Generally, it is preferable to adjust the stirring speed and time so that the monomer composition particles have a size of 30 μI or less. The rotation speed is 10 to 30 m at the circumferential speed of the turbine.
/sec, and the granulation time is not particularly limited, but is preferably 5 to 60 minutes.

When the liquid temperature during the granulation process is adjusted to a temperature at which the monomer composition has a viscosity of 1 to 1 million cps, preferably 100,000 to 100,000 cps, the particle size of the monomer composition particles can be adjusted to 1 to 10 μm. The final weight average particle size is 1 to 10μI.
A toner for development can be produced. As the liquid dispersion medium, water or an aqueous medium containing water as the main component is usually used.
The temperature of the dispersion liquid is 20 to 80°C (even 40 to 70t)
It is preferable that it is adjusted to.

In the dispersion liquid, it is preferable that the liquid dispersion medium is present in an amount of 200 to 100 parts by weight per 100 parts by weight of the monomer composition, and the slightly water-soluble inorganic dispersant is present in an amount of 200 to 100 parts by weight of the polymerizable monomer composition. 1 to 20% by weight (moreover, 1 to 20% by weight)
101i amount%) is preferably used.

Next, each component constituting the monomer composition will be explained.

Examples of the polymerizable monomer used in the present invention include CH2-, i.e., styrene, 0-methylstyrene, m-
Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene,
3.4-dichlorostyrene, p-ethylstyrene, 2.
4-dimethylstyrene, p-n-butylstyrene, p-
tert-butylstyrene% P-n-hexylstyrene, p-n-octylstyrene% Styrene and its derivatives such as P-n-nonylstyrene, P-n-decylstyrene, P-n-dodecylstyrene; ethylene , propylene, butylene, isobutylene, and other ethylenically unsaturated monoolefins; vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and other vinyl halide; vinyl acetate, vinyl propionate, vinyl benzene chloride, and other vinyl esters. Class: Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate
-octyl, dodecyl methacrylate, methacrylic acid-2
- α-methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylics, ethyl acrylate, n-butyl acrylate, acrylic acid Acrylic acid esters such as isobutyl, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate;
Maleic acid, maleic acid hafester; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone,
Vinyl ketones such as vinylhexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes;
Examples include acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylate trile, and acrylamide. These monomers can be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers as a polymerizable monomer in terms of the development characteristics and durability of the toner.

In order to improve the fixing properties and anti-offset properties in hot pressure roller fixing, the monomer composition contains release properties such as waxes such as paraffin wax, and low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene. (preferably a softening point of 50
In this case, the amount of the low softening point compound added is preferably 1 to 300 parts by weight per 100 parts by weight of the polymerizable monomer.

The above-mentioned low softening point compounds include paraffin, wax,
Low molecular weight polyolefins, modified waxes with aromatic groups, hydrocarbon compounds with alicyclic groups, natural waxes, long hydrocarbon chains with 12 or more carbon atoms (CHs (CHz)
Examples include long chain carboxylic acids having ++ or (aliphatic carbon chains of CH2112 or more), esters thereof, etc. Different low softening point compounds may be mixed and used.

Specifically, the low softening point compounds include paraffin wax (manufactured by Nippon Oil Co., Ltd.), paraffin wax (manufactured by Nippon Seiro Co., Ltd.), micro wax (manufactured by Nippon Seiro Co., Ltd.), microcrystalline wax (manufactured by Nippon Seiro Co., Ltd.), and hard paraffin. Wax (manufactured by Hiki Seiro), PE-130 (manufactured by Hoechst),
Mitsui Hiwax 110P (Mitsui Petrochemical), Mitsui Hiwax 220P (Mitsui Petrochemical), Mitsui Heiwax 660P (Mitsui Petrochemical), Mitsui Hiwax 210P (Mitsui Petrochemical), Mitsui Hiwax 32
0P (Mitsui Petrochemical), Mitsui Hiwax 410P
(manufactured by Mitsui Petrochemicals), Mitsui Hei Wax 420P (manufactured by Mitsui Petrochemicals), modified wax JC-1141 (manufactured by Mitsui Petrochemicals), modified wax JC-2130 (manufactured by Mitsui Petrochemicals), modified wax JC-4020 (manufactured by Mitsui Petrochemicals) Chemicals), modified wax JC-1142 (Mitsui Petrochemicals),
Modified wax JC-5020 (manufactured by Mitsui Petrochemicals); Examples include beeswax, carnauba wax, and montan wax.

In the monomer composition, in order to generate a crosslinked polymer,
Suspension polymerization may be carried out in the presence of a crosslinking agent, especially if no polymer, copolymer or cyclized rubber is added to the monomer composition. It is preferable to add it.

Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene 1, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1.3-butylene gelicold dimethacrylate, 1.6-hexane gelicold dimethacrylate, Neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate,
Polypropylene glycol dimethacrylate, 2.2'
-bis(4-methacryloxyjethoxyphenyl)propane, 2,2'-bis(4-acryloxyjethoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
General crosslinking agents such as tetramethylolmethanetetraacrylate, dibromneohentylglycol dimethacrylate, diallyl phthalate, etc. can be used as appropriate (two or more types in combination as necessary).

If these crosslinking agents are used in large amounts, the toner becomes difficult to melt with heat, resulting in poor heat fixing properties or heat pressure fixing properties. In addition, if the amount used is small, properties such as anti-blocking and durability required for toner will deteriorate, and during hot roll fixing, some of the toner will not completely adhere to the paper and will stick to the roller surface, causing the next paper to It becomes difficult to prevent the offset phenomenon of metastasis. Therefore, the amount of these crosslinking agents used is preferably o,oot to 15% by weight (more preferably 0.1 to 10% by weight) based on the polymerizable monomer.

The monomer composition contains a colorant, and dyes and pigments or magnetic particles are preferably used as the colorant.

As dyes and pigments, conventionally known dyes, carbon black, and pigments such as grafted carbon black in which the surface of carbon black is coated with a resin can be used (two or more types in combination as necessary). . Such dyes and pigments are contained in an amount of 0.1 to 30% based on the polymerizable monomer.

Charge control agents and fluidity modifiers may be added (internally added) to the toner as necessary, but when they are added internally,
The charge control agent and the fluidity modifier may be added to the monomer composition, but the charge control agent and the fluidity modifier may be used by being mixed (externally added) with the toner particles.

Examples of charge control agents include metal complexes of organic compounds having carboxyl groups or nitrogen-containing groups, metal-containing dyes, and nigrosine. Examples of fluidity modifiers or cleaning aids for the surface of the latent image carrier (FJ light body) include colloidal silica and fatty acid metal salts. In addition, fillers such as calcium carbonate and finely powdered silica may be added to the toner in a range of 0.5 to 20% by weight for the purpose of increasing the amount.Furthermore, it prevents toner particles from coagulating with each other and improves fluidity. To do this, a flow improver such as Teflon fine powder or zinc stearate powder may be incorporated into the toner.

To produce a magnetic polymerized toner, magnetic particles may be added to the monomer composition. In this case, the magnetic particles also serve as a colorant (in whole or in part). As magnetic particles, substances that are magnetized when placed in a magnetic field are used, such as powders of ferromagnetic metals such as iron, cobalt, and nickel, or powders of alloys and compounds such as magnetite, hematite, and ferrite. Magnetic fine particles having a particle size of 0.05 to 5 μm, preferably 0.1 to 1 μm are used. When producing toner with a small particle size (particle size of 8μ or less), it is preferable to use magnetic particles with a particle size of 0°8μ or less.The content of the magnetic particles is 100 parts of the monomer composition. 10 to 60 parts (and even 2 parts)
0 to 50 parts), and these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent, a titanium coupling agent, or an appropriate reactive resin. Although it depends on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, a treatment amount of 5 parts or less (preferably 0.1 to 3 parts) per 100 parts of the magnetic particles is sufficient to produce a polymerizable monomer. The dispersibility of the toner particles is obtained, and the toner physical properties are not adversely affected. Furthermore, lipophilic magnetic particles and hydrophilic magnetic particles may be used as a mixture.

According to the findings of the present inventors, when a water-soluble polymerization initiator is used, the polymerized toner produced is resistant to water. wealth decreases,
In order to produce a polymerized toner with excellent environmental properties, it is preferable to use a substantially water-insoluble polymerization initiator since the development characteristics and blocking resistance at high temperatures deteriorate.

As mentioned above, the polymerization initiator used in the present invention is preferably substantially water-insoluble. In the present invention, a substantially water-insoluble polymerization initiator refers to a polymerization initiator that is substantially water-insoluble at room temperature. It has a solubility of 1 g or less per 100 g of water, preferably 5 g or less per 100 g of water, particularly preferably 1 g of water.
It has a low solubility of 0.2g or less per 00g.

If the solubility exceeds 1 g per 100 g of water, it is not preferable because the decomposition products of the polymerization initiator remaining on the surface of the polymerized toner particles after completion of polymerization reduce the moisture resistance of the polymerized toner. The polymerization initiator used in
The polymerization initiator (1 to 10 parts by weight per 1 oz part of monomer) preferably has solubility characteristics that allow it to dissolve well in the polymerizable monomer.

As such a polymerization initiator, 2,2'-azobis(
2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-
Azo or diazo polymerization initiators such as 4-methoxy-2゜4-dimethylvaleronitrile and other azobisisobutyronitrile (AIBN): benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxy carbonate, cumene hydroper Examples include peroxide-based polymerization initiators such as oxide, 2,4-dichlorylbenzoyl peroxide, and lauroyl peroxide.

Furthermore, it is also preferable to use a mixture of two or more types of polymerization initiators for the purpose of adjusting the molecular weight and molecular weight distribution of the polymer, or for the purpose of adjusting the reaction time.

The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerization monomer. If the amount of the polymerization initiator used is less than 0.1 parts by weight, It is difficult to uniformly disperse or apply a sufficient amount of the polymerization initiator to each monomer composition particle, and if it is 20 parts by weight or more, it is too much and the molecular weight of the polymerization product becomes too low.
The tendency for polymerization reactions to occur heterogeneously increases.

Such a polymerization initiator can be added to a dispersion system containing monomer composition particles after granulating the monomer composition, but it is possible to add the polymerization initiator to a dispersion system containing monomer composition particles evenly. From the viewpoint of dispersing or applying the initiator, it is preferable to include it in the monomer composition before granulation.

The suspension polymerization reaction is usually carried out at a polymerization temperature of 50° C. or higher, and the upper limit temperature is set in consideration of the decomposition rate of the polymerization initiator. If the set polymerization temperature is too high, the polymerization initiator will be rapidly decomposed, which is not preferable.

In the present invention, after confirming that the formed monomer composition particles have a predetermined particle size, polymerization is carried out by adjusting the liquid temperature (for example, 55 to 70°C) of the aqueous medium containing the particles. A method for advancing the reaction, or a method for advancing polymerization simultaneously with granulation and dispersion by adjusting the liquid temperature of the dispersion medium is used.

After the polymerization reaction of the monomer composition is completed, polymerized toner particles can be obtained by post-treatment using a conventional method. After removing the dispersant, the polymer particles are recovered by a suitable method such as filtration, decanting, centrifugation, etc. and dried to obtain a polymerized toner.

The Brønsted acid-soluble poorly water-soluble inorganic dispersant used in the present invention can be easily removed from the toner particle surface by the above-mentioned acid (or alkali) treatment.

In the toner from which the dispersant has been removed in this way, there is no adverse effect of hydrophilicization of the toner surface (due to the residual dispersant), and good toner development characteristics can be obtained.

The polymerized toner obtained by the production method of the present invention can be applied to known dry electrostatic image development methods, such as cascade method,
Two-component development methods such as magnetic brush method, microtoning method, two-component AC bias development method: conductive-component development method,
One-component development methods using magnetic toner, such as insulating-component development method and jumping development method; powder cloud method and fur brush method; toner is transported to the developing section by being held on the toner carrier by electrostatic force It is applicable to a non-magnetic component development method in which the toner is transported to a developing section and subjected to development; and an electric field curtain development method in which the toner is transported to a developing section and subjected to development.

The toner obtained by the method of the present invention can be particularly preferably applied to a developing method using a toner with a small particle size of 2 to 8 μm in terms of weight average particle size, which requires a sharp particle size distribution.

11 Danri 1 As described above, according to the method for producing a polymerized toner of the present invention, a poorly water-soluble inorganic fine powder in a dispersion medium and a polar substance in a monomer composition are used to disperse the composition/dispersion. By achieving a preferable interfacial tension between the media, monomer composition particles can be formed in a suitable state, and a polymerized toner with a sharp particle size distribution and good development characteristics can be obtained in good yield.

Hereinafter, the present invention will be explained in more detail based on Examples.

Nas po4.1 in 100100O of ion-exchanged water
2m (25.5g of 20 was added and stirred at 10,000 rpm using a TK homomixer (Tokushuki Kakosai). CaCj2z 2) (20) was dissolved in 14.2g of ion-exchanged water (200IIIt) to form an aqueous solution of the above solution. Na3
It was gradually added to the po4 solution while stirring with the homomixer to obtain a dispersion medium (p)I-10,5) containing calcium phosphate, which is a poorly water-soluble inorganic fine powder. When measured using a Coulter counter, in the number distribution of the fine powder, the proportion of particles with a particle size of 4.0 μm or more was 1% or less in number.

and mix at 60℃! #mer composition (viscosity 300 cps at 60°C) was prepared.

The jIL mass composition obtained above was placed in a stainless steel container with a capacity of ff12j2 containing the dispersion medium containing calcium phosphate prepared as described above, and the mixture was heated for 60 minutes under an N2 atmosphere.
℃ using a TK homomixer (Special Machinery and Industrial Vegetables),
0. The monomer composition was granulated by stirring at OOO rpm for 30 minutes. Thereafter, the monomer composition was polymerized at 60° C. for 10 hours while stirring with a paddle stirring blade.

After the above reaction is completed, the reaction product is cooled, dehydrated, and hydrochloric acid (
1/ION), further washed with water, dehydrated, and dried to obtain a polymerized toner. When the particle size of the obtained toner was measured using a Coulter counter (aperture diameter: 100 μm), the volume average diameter was 8.5 μl, and the particle size distribution was extremely narrow.

15 g of the toner obtained above and an average particle size of 50 μm
85 g of insulating carrier (composed of triiron tetroxide and epoxy resin), 0.75 g of hydrophobic silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.), and 0.45 g of zinc stearate powder were mixed to form a developer. was prepared, and its electrophotographic properties were evaluated under the following conditions.

A developing device whose schematic cross-sectional view is shown in the drawing was used as a developing device.

The image carrier 1 has a selenium photoreceptor 11, the peripheral speed of the image carrier 1 is 100III/sec, and the highest potential of the electrostatic image formed on the image carrier 1 is +750V.

The outer diameter of the sleeve (developer carrier) 2 is 20tm,
Its circumferential speed is 100 arm/sec, and the magnetic flux density in the vertical direction of the sleeve surface of the N and S poles of the magnet roller 3 is 100 arm/sec.
0 Gauss, developer layer thickness 200 μm, gap between sleeve 2 and image carrier 1 300 μ1%, bias voltage applied to the sleeve has DC voltage component +200V, AC voltage component 3.
When I developed it at 1400Vpp with 0KIIZ,
The electrostatic latent image on the image carrier 1 was developed well.

The toner image formed by this development is electrostatically transferred onto plain paper, and the toner image on the plain paper is transferred to a heat-pressure roller fixing device 7 consisting of a fixing roller having a silicone rubber surface layer and a pressure roller. Under pressure of 87cm”, nip width 9
This toner image was fixed well at a fixing temperature of 150° C. (fixing roller surface temperature). The obtained fixed image has no fog and image density (D max)
It showed 1.44.

In addition, in the developing device shown in the drawing, external additives (silica powder, etc.)
The toner T having the following properties is quantitatively supplied to the lower chamber by the supply roller 4 and the elastic member 5, and is mixed with the carrier to form the developer 6. DC bias is applied from a DC bias power source 8 to the sleeve 2 containing the magnet roller 3 and the doctor blade 7.
AC bias is applied from an AC bias power supply 9. As the sleeve 2 rotates in the direction of
The electrostatic latent image on the image bearing member 1 is developed. The developer layer regulating member 10 also serves as an outer wall of the developing device.

In addition, 90 g of styrene, 10 g of 2-ethylhexyl methacrylate, 10 g of cyclized rubber, and Bontron E-81.
, 2g of NK ester 2G and 11g of NK ester 2G, the interfacial tension (interfacial tension (A)) with respect to the dispersion medium containing calcium phosphate prepared above was measured using a surface tension measuring device (yow) using the method described above. ^、CBVP
It was measured at room temperature (215° C.) using a 5 surface Tension Meter^3).

This interfacial tension (A) was 2.0 dyne/cm.

On the other hand, when the interfacial tension (B) of the above model composition with respect to ion-exchanged water was similarly measured, it was found to be 3°2 dyne.
/cm.

(treated with 3 parts of BrenAct KR-1385 manufactured by Sosha Co., Ltd.) The above polymerizable monomer mixture was treated with 60%
The monomer composition (viscosity at 60°C: 80
0 cps) was prepared.

In a stainless steel container with a capacity of 2jZ, the monomer composition obtained above was added to a dispersion medium containing calcium phosphate prepared in the same manner as in Example 1, and the monomer composition was heated to T at 60°C under an N2 atmosphere.
10,0O using K homo mixer (Special Kika Kogyo)
The mixture was stirred and granulated using Orp+a for 30 minutes. The monomer composition was then polymerized at 60° C. for 20 hours using paddle blade stirring.

The above reaction product was cooled, dehydrated, and hydrochloric acid (1/1 ON)
A polymerized toner was obtained by washing with water, dehydration, and drying. When the particle size of the obtained toner was measured using a coulter counter (Avachair diameter: 100 μl), the volume average diameter was 9.5 μl, and the proportion of coarse powder of 16 μm or more in the volume distribution was 3% by volume, which was extremely low in particle size distribution. It was narrow.

0.6 g of hydrophobic silica (Talanox-5001 manufactured by Talco) was mixed with 100 g of the toner obtained above.
A developer was prepared.

When this developer was applied to a Canon copier NP-7550 and an image formation test was conducted at room temperature (25° C., 60%), images with good image quality and density were obtained.

When images were produced in the same manner as above at 32.5°C and 90% high temperature and high humidity, images with good quality and density were obtained.

11 ■ Add 30.8 g of Na=po4 hydrated salt (Na3 PO4' 12H20) into 100,100 O of ion-exchanged water, and use a TK homomixer (Tokushu Kika Kogyo) to mix
．． Stirred at 0OOrpn+.

AJ2z (SO4)3 hydrate salt (Aftz (SO
4) 29g of 3.50% content) 200g of ion-exchanged water
! The aqueous solution dissolved in LIt was gradually added to the above N83PO4 solution while stirring with the above homomixer, and a dispersion medium (pH-
3,8) were obtained.

When the particle size of the fine powder in this dispersion medium was measured using a Coulter counter, the proportion of particles with a particle size of 4.0 μm or more was 1% in number.

The above polymerizable monomer mixture was mixed with 6 ml using an attritor.
By mixing at 0°C, the monomer composition (viscosity at 60°C: 30
0 cps) was prepared.

The above monomer composition was placed in a stainless steel container with a capacity of 21 containing the dispersion medium containing aluminum phosphate prepared above, and treated in the same manner as in Example 1 to obtain a volume average diameter of 8 μm.
I got the toner.

A developer was prepared by mixing 0.6 g of hydrophobic silica treated with amino-modified silicone oil with 100 g of the toner obtained above. Use this developer on a Canon copier NP-35.
When image printing was carried out using No. 25, images with good image quality and density were obtained at room temperature. Also,
Similarly good images were obtained even under high temperature and high humidity conditions of 32 ++ 5°C and 90%.

Add Na, cow anhydrous salt (N
8.91 g of a2 COs ) was added and stirred at 10,000 rpm using a TK homo mixer (Tokushu Kika Kosai Rui). 11.3g of ZnCA2 anhydrous salt (ZnCU, )
The above Na
pCo was gradually added to the solution while stirring with the homomixer to obtain a dispersion medium (pH=about 7.5) containing ZnCO3. When measured with a Coulter counter, the above Zn
The volume average diameter of CO5 is 2.9μ■, and the particle size is 4.0μ■
The proportion of the above particles was 1% or less in number.

A toner was obtained in the same manner as in Example 2, except that the dispersion medium containing ZnC0 obtained above was used.

The particle size of the obtained toner was measured using a Coulter counter, and the volume average diameter was 8.5 μm. Using this toner, image printing was performed in the same manner as in Example 2.
Images with good quality and density were obtained.

Ki Ko 1 Na1COs anhydrous salt 8.4 in ion exchange water 10100O
6 g was added and stirred at 10,000 rpm using a TK homo mixer (Tokushu Kika Kosai). ZnCJE□12.3g of anhydrous salt and 200mj of ion-exchanged water! A solution dissolved in the above Na, Co.

Gradually add ZnC to the solution while stirring with the homomixer mentioned above.
A dispersion medium (pH=about 5.8) containing 0.0 was obtained. When measured using a Coulter counter, Z in the above dispersion medium
The volume average diameter of nC0, is 2.9 μ-, and the particle size is 4.08
The proportion of particles of 1 or more was 1% or less in number.

A toner was obtained in the same manner as in Example 3, except that the ZnCO3-containing dispersion medium obtained above was used.

The particle size of the obtained toner was measured using a Coulter counter, and the volume average diameter was 9.5 μm. When this toner was used to produce an image in the same manner as in Example 3, a □ image with good image quality and density was obtained.

Ki 1 ion exchange water 500mA and Na200w anhydrous salt 4.23
10. Stirred at OOO rpm. A solution in which 6.15 g of ZnCjZ2 anhydrous salt was dissolved in 200 g of ion-exchanged water was gradually added to the above N82COs solution while stirring with a homomixer to obtain a dispersion medium containing ZnCOS.

Meanwhile, in another container, Na2 CO
s 5.25g of anhydrous salt and CaCj! Dihydrate salt (CaCA
A dispersion medium containing CaCO5 was obtained using 9.8 g of 2.2H20).

The two dispersion media, the ZnCCl3-containing dispersion medium and the CaCO3-containing dispersion medium obtained above, were mixed to obtain a dispersion medium (pH-about 5.8) used in this example.

The volume average diameter of the inorganic fine powder in this dispersion medium was 2.9 μm.

A toner was obtained in the same manner as in Example 3 except that the dispersion medium thus obtained was used. The volume average diameter of the obtained toner was 9.0 μI.

Ehodan Yuion exchange water 800mj! Na2COs anhydrous salt 9.9
Add 8g and mix with TK homomixer for 10,000
* Z n c x 2 anhydrous salt 5.8 stirred at rp
A solution in which 5 g of ion-exchanged water was dissolved in 200 ml of ion-exchanged water was gradually added to the above Na2Co@ solution while stirring with a homomixer to obtain a dispersion medium containing ZnCO5.
A solution of 9.8 g of dihydrate salt dissolved in 200 mA of ion-exchanged water was gradually added to the above dispersion medium while stirring with a homomixer to obtain a dispersion medium containing CaC0 and ZnCO5 (pH - about 7°5). Ta.

The volume average diameter of the inorganic fine powder in this dispersion medium was 2.7 μm.

A toner was obtained in the same manner as in Example 2 except that the dispersion medium obtained above was used. The volume average diameter of the obtained toner was 10.5μ
It was Cao.

K151 Ion exchange water 10001111 N as P 04
30.8 g of hydrated salt was added, and the mixture was stirred at 10.0 OOrp using a TK homo mixer (Tokushu Kika Kogyo).

A solution of 28 g of AlI3 (304)s hydrated salt dissolved in 200 μA of ion-exchanged water was gradually added to the above Na5PO4 solution while stirring with a homomixer to obtain a dispersion medium containing aluminum phosphate (pH 4.5). Ta.

The particle size of aluminum phosphate in this dispersion medium is
When measured using a counter, the proportion of particles with a particle size of 4.0 μm or more was 1% in number.

A polymerized toner was obtained in the same manner as in Example 3, except that the dispersion medium obtained above was used.

When image formation was carried out in the same manner as in Example 3 using this polymerized toner, a good image was obtained as in Example 3.

Egoryu ion exchange water 10100O to Na5PO4”12H20
24.5 g was added and stirred at 110,000 rpm using a TK homo mixer (Tokushu Kika Kogyo). CaCj
! * 62H2014゜2g ion-exchanged water 200ml
The solution dissolved in -A was gradually added to the above Na3PO4 solution while stirring with a homomixer to obtain a dispersion tA (+)H-10,5) containing calcium phosphate. When the particle size of the calcium phosphate was measured using a Coulter counter, the proportion of particles with a particle size of 4.0 μm or more was 1% or less in number.

In place of 10 g of cyclized rubber in Example 1, a polyester (acid value 10, hydroxyl value 15) which is a condensation product of etherified diphenol, terephthalic acid, and trimellitic anhydride was used.
The same composition as in Example 1 was used except that 10 g was used,
In addition, the same procedure as in Example 1 was performed except that the calcium phosphate-containing dispersion medium obtained above was used, and the volume average diameter was 8.5.
I got the μen toner.

When this toner was used to produce an image in the same manner as in Example 1, a good image was obtained as in Example 1.

Back 1 ■ Add 30.8 g of Nas PO4 hydrated salt to 1000 mjl of ion-exchanged water, and mix using a TK homo mixer (Tokushu Kika Kogyo). 10. Stirred at OOOrpm*
Aj2z (SO4)s 28 g of hydrated salt -i't exchange water Exchange water 200 tons! The above Na, PO4
It was gradually added to the solution while stirring with a homomixer to obtain a dispersion medium (p) lx4.5) containing aluminum phosphate.

The particle size of aluminum phosphate in this dispersion medium is
When measured using a counter, the proportion of particles with a particle size of 4.0 μm or more was 1% in number.

A monomer composition was polymerized in the same manner as in Example 1 except that the dispersion medium obtained above was used, but a stable granular polymer could not be obtained.

Na3PO4-12H in 1000+afL of ion-exchanged water
4.5 g of iO2 was added and stirred at 10,000 rpm using a TK homo mixer (Tokushu Kika Kosai).

CaCu2 $ 2H2014゜2g ion-exchanged water 2
A solution dissolved in 00mj2 was gradually added to the above Na, PO4 solution while stirring with a homomixer, and then 0.15 g of a 20% aqueous solution of sodium dodecylbenzenesulfonate was added to obtain a dispersion medium containing calcium phosphate. . When the particle size of calcium phosphate was measured using a Coulter counter, the proportion of particles with a particle size of 4.0 μm or more was 1% or less in number.

A toner was obtained in the same manner as in Example 2 except that the dispersion medium obtained above was used.

After classifying the obtained toner into a volume average diameter of 9.5 μm,
When an image was produced in the same manner as in Example 2 using this classified toner, only a rough image was obtained at 32.5° C. and 90% high temperature and high humidity.

The interfacial tension (A) between the monomer composition used in each of the Examples and Comparative Examples above (model composition) from which the colorant has been removed and the dispersion medium, and the model composition and ion-exchanged water. The interfacial tension (B) was measured in the same manner as in Example 1.

The following results are obtained from the values of these interfacial tensions (A) and (B) at the interfacial tension measurement temperature (room temperature).
These are measurement results obtained using a model composition that does not contain a polymerization initiator and paraffin wax at 155°F, which may adversely affect measurement results.

[Brief explanation of the drawing]

The drawing is a schematic cross-sectional view showing a developing device used in Examples. 1... Image carrier 2... Sleeve 3... Magnet roller 4... Supply roller 5... Elastic member 6... Developer 7... Doctor blade 8.9-... Bias power supply 10...Developer layer regulating member C″″-Σ

Claims (1)

[Claims] Contains a poorly water-soluble inorganic dispersant powder soluble in Brønsted acid, has a pH in the range of 2.5 to 6.0 or 7.1 to 11.0, and substantially A method for polymerizing a monomer composition containing at least a polymerizable monomer, a polar substance, and a colorant in a dispersion medium that does not contain a water-soluble surfactant; The interfacial tension (A) between the composition excluding the colorant and the dispersion medium is 95≧(B-A)/B×100≧5 (in the above formula, B represents the coloring from the monomer composition). (Represents the interfacial tension between the composition excluding the agent and ion-exchanged water.)
A method for producing a polymerized toner characterized by satisfying the following relationship.