JPH03214168A - Electrophotographic toner - Google Patents

Abstract

PURPOSE:To improve humidity dependency of electric charging characteristics, fluidity, insulation property, and the like, and to enhance fixability, sharp meltability, and offset resistance by incorporating a resin base composed essentially of polyester specified in softening point and glass transition point and specifying >=70 number average % of particle distribution to be over 0.7 in the sphericity. CONSTITUTION:The polyester resin to be used for the main component of the resin base has a softening point of 80-150 deg.C and a glass transition point of >=40 deg.C, and the resin particles having a sphericity (longer diameter to shorter diameter ratio) of >= 0.7 exist in an amount of >=70 number average %, and the polyester mainly composed of dicarboxylic components and glycol componets is preferable, thus permitting the obtained electrophotographic toner to be improved in the humidity dependency of charging characteristics, fluidity characteristics, insulation property, and the like and to be enhanced in fixability, sharp meltability, and offset resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to toner. More specifically, the present invention relates to a toner used as a developer in electrophotographic copying machines, laser printers, and the like.

(Prior art) ・In general, the electronic printing method refers to inorganic systems such as selenium, amorphous silicone, and zinc oxide, or diaso compounds, and organic systems (often added in the form of a drum). A photoconductive material (photosensitive drum) is first charged in a negative manner, and then an electrostatic latent image is formed by irradiating it with image-modulated light. The image is developed by attaching the powder, and if necessary, the powder is transferred to a base material such as paper or film, and then fixed using methods such as pressure and heating.Currently, the electrophotographic method is Widely used in copying machines, laser printers, etc.

In electrophotography, a powder that develops an electrostatic latent image on a photosensitive drum E and is finally transferred to a base material such as paper or film to form an image is called a toner. These toners are usually mixed with carrier particles (carrier) such as glass beads, iron powder, ferrite, etc., and used as a so-called developer.

Conventionally, toners used in I-Ryo photo developers include:
A so-called pulverization method has been used, which involves adding colorants, charge control agents, fluidity modifiers, grinding aids, etc. to thermoplastic resins, kneading them, pulverizing them, and then classifying them. . Or, in recent years, toner research has been carried out using Emul/Nine Thousand Law, Suspended Legal Node + TI: Legal, etc.1).

These toners are required to have various physical or chemical properties.

As mentioned above, the image copying process in the electric f "j" f:c system consists of repeated electrostatic transfer of charged toner. Therefore, there are many requirements regarding the charging characteristics of toner. Various methods have been proposed and put into practical use to charge the toner, but in many cases, it is difficult to combine the toner with carrier particles (carrier), which are mixed together to form the developer. A common method is to charge by friction. In this case, it is desirable that the toner charging factor be a constant value regardless of the degree of friction or time. This is because when the toner charge level changes, the toner M adhering to the electrostatic latent image 1- on the photosensitive drum changes, resulting in a one-degree fluctuation in the copied image.

on the carrier)'! In order to quickly perform the rubbing process, it is also necessary to quickly transfer the electrostatic latent image of the photosensitive drums L, L, or from the photosensitive drum A l'' to paper or film substrates. In order for this to occur, it is of course necessary that the toner has good flowability.

The electrostatic latent image toner on the photosensitive drum 1- is bonded by electrostatic force. Therefore, when transferring from a photosensitive drum to a base material such as paper or a film book, a bias voltage may be applied to the base material side. The base material and toner need to have sufficient insulation to withstand this voltage. In many cases, the insulation properties of paper used as a base material are greatly reduced by humidity. Therefore, this insulating property is solely responsible for the ``Haimi Totona''.

The toner transferred onto the base material is fixed by heating, pressure, or the like. The heated or pressurized toner needs to quickly melt or plastically deform and adhere to the base material.

At this time, the quality of the image must not be degraded by lowering the viscosity by more than 1, which is necessary. At the same time, constant n
Attached to the roll side? There should be no such thing as doing something like that.

The characteristics required of these toners described in 1.
1. Due to the natural scarcity, long-term maintenance /7. In addition, it must not change even after repeated use. N photo 1! ! Even after becoming a II image, image quality must be maintained for a long period of time. Also, there must be no transfer or transfer to other locations.

When copying both color images, it is necessary to prepare toners for each of the three subtractive primary colors, cyan, magenta, and yellow. These color toners each need to have predetermined reflection spectral characteristics, similar to process inks for printing.

In recent years, in order to improve the quality of copied images, there is a tendency for toners to have smaller particle diameters and sharper 71x degree distribution.

Furthermore, it is out of the question that these toners that form the copied images themselves contain toxic and deleterious ingredients that are harmful to the human body and impair health.
I need to! : That's not even Kei.

(Problems to be Solved by the Invention) The characteristics required of toner have been described above, but the toners conventionally used do not completely satisfy them.

With many toners, during repeated development due to continuous use, collisions between the toner and carrier particles and contact between these particles and the photosensitive drum surface cause mutual deterioration of the toner, carrier particles, and photosensitive drum surface. As the degree changes or the height increases by 1 degree, the image quality deteriorates.

Attempting to increase the density of a reproduced image by increasing the amount of toner particles deposited on the electrostatic latent image on the photosensitive drum usually results in an increase in background density. Cow the so-called Kabuli.

When toner is transferred from an electrostatic latent image on a photosensitive drum to a substrate such as paper by applying a bias voltage, the toner must have sufficient insulation, especially in situations where the insulation of the substrate has decreased due to the influence of humidity. Because I haven't done it myself, I've used Photosensitive Drano 4. A discharge occurs between the photosensitive drum 1° and the -1i/;r of the photosensitive drum is neutralized, so the electrostatic latent image is destroyed, and the toner adhering to the static latent image is scattered and II' As a result, the quality of the copied image is extremely low (so-called self-indulgence)! : There is.

To + - transferred to paper or film substrate 1.
Regarding fixing, it is necessary to strictly control the degree of softening of the toner, and more specifically, the relationship between temperature and melt viscosity. More specifically, it is required to have the so-called sharp melt property, which functions as a solid up to a constant M f & 1 degree and melts quickly at a predetermined temperature, but it is difficult to achieve this. In reality, fixing is currently performed at considerably high temperatures.

Furthermore, because the fixability to the base material is prioritized, it is difficult to say that there is no adhesion to the fixing roll.

In order to solve this problem, in many cases, it is advised not to apply a release aid such as recon oil to the fixing roll. In that case, the problem arises as to whether the release aid adheres to the base material. In addition, it becomes troublesome to periodically replenish the 9Mi auxiliary agent and maintain the device.

Toners with a low degree of softening temperature tend to aggregate during handling or storage due to their property of being easily melted by heat, and their fluidity deteriorates significantly, especially during long-term storage.

Also, many toners are affected by the temperature of the environment.
Its friction zone centering and flow properties deteriorate.

In order to improve the quality of copied images, toners with smaller particle diameters have been strongly demanded in recent years, and the issue of manufacturing cannot be left out of discussion. In other words, it is difficult to industrially obtain particles with an average particle size of about 10 particles or less using the pulverization method that has traditionally been used as a method for manufacturing toner. If so, it is not so difficult to obtain particles of 10 or less sizes using the current crusher.

However, since not all of the pulverized particles have the desired particle size, a classification operation is naturally required. This means that the minute retention rate will drop significantly. Furthermore, in the case of producing a small-particle-sized horse chestnut by the pulverization method, -1: component heat II) a blue agent added to the plastic resin, a preform control agent, a fluid t' [modifier, a pulverization aid It is necessary to prepare and crush the toner to a particle size smaller than the required size, which inevitably increases the manufacturing cost.Perhaps for these reasons, manufacturing of toner with a fine particle size by the pulverization method is not possible. 1. This makes it difficult to establish and implement commercially.

By the crushing method? The shape of the toner to be produced is naturally amorphous, and only those exhibiting broad particle size distribution can be obtained.

In recent years, research on toners using emulsion polymerization methods, suspension polymerization methods, 71-day city methods, etc., conducted in the department, has been conducted.
This method has been carried out with the aim of addressing the problems of the pulverization method mentioned above.The particles obtained by the small method have excellent fluidity because of their spherical shape, and therefore have uniform friction. It can be expected to have excellent properties such as the ability to control the heat melting properties by appropriately controlling the small groups.

In the emulsion polymerization method, polymerization is carried out in micelles of polymerizable monomers stabilized with a surfactant in water to obtain fine powder particles.

In the emulsion polymerization method, it is possible to obtain particles with a 7-yave particle size distribution of 4-r. However, since the particle size is determined by the size of micelles that can stably exist, the particle size is limited to a range of approximately 0.01 to 0.5-, and particles having a particle size of approximately 1) is difficult to create.

Since the particle size required for toners is limited to approximately several to several dozen, particles obtained by emulsion polymerization cannot be used as they are in electrophotographic toners. Furthermore, if a surfactant essential for stabilizing micelles remains on the particle surface, it may affect the fluidity or charging characteristics of the particles.

A suspension polymerization method is a method in which particles are obtained by combining polymerizable monomers in a suspension system obtained by stirring water and polymerizable monomers. In the suspension polymerization method, it is not easy to perform polymerization in a stable system, and it is technically difficult to form fine small aggregates with a uniform particle size distribution by one polymerization (1)). The reason for this is that the grains are combined during granulation. In order to prevent the coalescence of the molecules and stabilize the combination, for example, in suspension synthesis, when the commercially available compound is polymerized in an aqueous dispersion system, as the polymerization progresses, , a suspension stabilizer is used to prevent coalescence. ! ! ! The turbidity stabilizer is generally a sparingly soluble inorganic compound, such as sparingly soluble salts such as barium sulfate, calcium sulfate, magnesium carbonate, barium carbonate, calcium carbonate, phosphoric acid, silica, calcia, magnesia, titanium oxide, etc. Metal oxides, minerals such as diatoms, talc, concretions, and kaolin, and mixtures thereof, or water-soluble mixtures such as polyvinyl alcohol, gelatin, starch, etc. are used. It is known that these suspension stabilizers have a negative effect on the charging characteristics of particles if they remain on the particle surface, so cleaning etc. are essential after obtaining Sengo-Gun-r, but they must be completely removed. It is very difficult to remove. In fact, even when these suspension stabilizers are used, I! ! The particle size range of the particles obtained by cloudy/nonconforming lL is about several i-p to J-, and the particle size distribution is also broad, so the particle size range required for electrophotographic toners is approximately several p to J-. It is difficult to obtain a particle size in the range of 7000.

The seed polymerization method is a polymerization method proposed to solve these problems. In the seed polymerization method, for example, the seed particles obtained by other methods such as the Emulnoyon polymerization method are used as seed particles, the seed particles are swollen with a solvent and a polymerizable monomer, and the seed particles are polymerized in the swollen seed particles Y. This is a method of growing the seed grains Y by doing this. In the seed polymerization method, by selecting appropriate seed particles, particles having a particle size distribution of 7.5 mm can be obtained. Further, the particle size of the particles can be controlled by the swelling ratio of the seed particles and the polymerizable monomer.

However, the swelling rate of the seed particles cannot be increased unnecessarily. For example, increasing the particle size by a factor of 1 is equivalent to increasing the volume by a factor of 1,000. When the seed particles are swollen approximately twice as much by the polymerizable intermediate, the seed particles may be able to maintain their particle shape, or in some cases may collapse. In other words, there is a natural limit to the particle size range in which the swelling rate can be increased to an extremely large degree (2 to 3 degrees).
It's about double that. In order to grow larger particles, it is necessary to repeat the seed polymerization.

In seed polymerization, it is technically possible to obtain grains having a soarp particle size distribution in the particle size range of several to several. However, it is not easy to find a suitable particle size for the seed grains I, and the manufacturing cost is enormous due to the complexity of the process. It can't be a method.

In other words, the number required for electrophotographic toner is
It is extremely difficult to industrially produce particles with a sharp particle size distribution in a particle size range of 7000 at a low cost using conventional polymerization methods.

Furthermore, in the conventional f-polymerization method, 1) the resin particles r- are typified by styrene/acrylic resin, etc.
It is limited to so-called vinyl resin particles.

Furthermore, the resin particles obtained by one of these methods are provided with many physical properties that are essential for electrophotographic toners (charge control agent used for sipping, coloring agent, anti-offset agent, flowability agent 1). It is not easy to add such substances.In other words, even in the resin particles obtained by the conventional tensioning method, many of the problems required for toners have not yet been solved.

As described below, conventional toners have moisture resistance, that is, humidity dependence such as charging characteristics, flow characteristics, and insulation, as well as fixing properties, sharp melt properties, offset resistance, particle size distribution, color reproducibility, Furthermore, it had many problems such as manufacturing cost.

In view of this situation, the inventors of the present invention have conducted extensive research in order to obtain a toner that comprehensively satisfies many of these required characteristics and can be produced industrially, and as a result, they have arrived at the following invention.

(Step 1 for solving the problem) That is, the present invention uses a resin (A) having a softening point of 80 to 150°C as a base material and a polyester having a lath transition point of 40°C or higher as -L component 3. An electrophotographic toner characterized by having a number average of 70% (1) of particles having a sphericity (ratio of major axis to minor axis) of 0.7 or more. The toner is further characterized in that the toner is colored blue by pigment 4.The toner of the present invention is made of a specific resin or base material of polyester 13,
The characteristic color is that particles with a sphericity of 0.7 or more -r- are present in number/V average and 70% or more, but the average particle size is 1 to 30- Definition 0 when particle size is D
．． It is preferable to have a sharp particle size distribution in which 70% or more of particles having a particle size falling within the range of 51) to 2.01) exist on average.

In the present invention, the substance 1) whose sphericity (ratio of major axis to minor axis) is 0.7 or more - [- is present in 70% or more in terms of Fi
If the average particle size is 1), the number average of particles with a diameter in the range of 0.50 to 21) is 70% of the total.
The method for obtaining polyester-based resin particles having a uniform particle size distribution of more than 7% is, for example, an aqueous dispersion containing an ionic) A3 polyester as the L component, and the counterionic group of the resin. The vinyl monomer containing a is 0.8 to 2. An example of a method for manufacturing by aggregating O can be exemplified.

Here, the polyester is not particularly limited, but F is preferably a polyester consisting of a dicarboxylic acid resin and a glycol component.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid, and aromatic oxycarboxylic acids such as p-oxybenzoic acid and p-(hydroxyethoxy)benzoic acid. ,
Aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid,
These include tetrahydrophthalic acid, exclusively unsaturated aliphatic, and cycloaliphatic dicarboxylic acids.

Trino'I't) acid, trimenoic acid, if necessary
It may also contain a small amount of tri- and tetracarboxylic acids such as pyromellitic acid.

Glycol components include, for example, ethylene glycol, propylene glycol, l,3-propantool, l,
4-butanol, 1,5-pentanol, i
, e-hexaneol, neopentyl glycol,
noethylene glycol, nobropyre/glycol, 2,
2.4-) riftyl-1,3-pencundiol, 1,
Diols such as 4-cyclohexa/dimetta-7ol, spiroglycol, 1゜4-phenylene glycol, ethylene oxide adduct of L4-phenylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bispher/-A There are ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, ethylene oxide adducts and hyfurobylene oxide adducts of hydrogenated bisphenol A, etc.

A small amount of trimethylol ethano, trimethylolpropane, gelithin, pe/taerthritol, and tetraol may be contained in a small amount.

Other examples of polyester polyols include lactone-based polynisdel polyols, which are obtained by ring-opening polymerization of lactones such as ε-cabrolactone.

Ionic groups contained in polyester include anionic groups such as carboxyl groups, sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, or salts thereof, or cationic groups such as primary to tertiary amine groups. and preferably a sulfonic acid group and its metal base.

Examples of aromatic dicarboxylic acids containing a sulfonic acid group and its metal base that can be copolymerized with HoIJ ester include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7 dicarboxylic acid, [
Examples include 4-sulfofenoquine] isophthalic acid and its metal salts. Examples of metal salts include LisNa, MgtCa, (U, Fe''1'I salts). Particularly preferred is 5-strinesulfiptalic acid.

As long as a fine particle dispersion system, especially an aqueous dispersion, is obtained for the acid or its metal base-containing aromatic nocarboxylic acid, no limitation is recognized in 6), or approximately 20 to 500
Appropriate: within the range of i+/1000000g.

In the present invention, the polyester resin may be of type A or, depending on necessity, two or more types of polyester resins may be used in combination.

Further, it can be mixed with amino resins, epoxy resin isocyanate compounds, etc. in a molten state or a solution state, and furthermore, it can be partially reacted with these compounds. Similarly, the obtained partial reaction product can also be used as a raw material for an aqueous dispersion.

The aqueous dispersion containing the ionic group-containing polyester of the present invention as the L component can be produced by any known method. That is, either polyester and a water-soluble compound are warm-mixed at 50-200°C, and water is added to this, or a mixture of polyester and a water-soluble compound is added to water, and the mixture is heated at 40-120°C. Manufactured by stirring.

Alternatively, polyester is added to a mixed solution of water and a water-soluble compound, and the mixture is stirred at 40 to 100°C.

It can also be produced by the method of dispersing.

In the present invention, "a vinyl monomer having a counterionic group" refers to an ionic group opposite to the ionic group contained in the polyester (a counterion when the ionic group contained in the polyester is an anionic group). The ionic group is a cationic group,
Further, when the ionic group contained in the polyester is a cationic group, the counterionic group means a vinyl monomer having an anionic group. Such ionic groups are preferred in 1- to form stable aqueous dispersions of polyester.

The counterionic group bottle has an equivalent ratio of 0.8 to 2 of the counterionic group in the polymer obtained by polymerizing vinyl polymerizable heptamer to the ionic group in the polyester. .0
, preferably in the range of 0.85 to 1.5. If the limit of this range is not reached, coalescence and growth of fine particles will be difficult to occur, and even if the limit of 1 is exceeded. Not only is this not conducive to the growth of resin powder, it may also cause problems such as low water resistance of the resin powder.

Examples of the vinyl monomer containing an ionic group include 2
-Aminoethyl (meth)acrylate, 2-N,N-dimethylamineethyl (meth)acrylate, 2-N,N
-diethylaminoethyl (meth)acrylate, 2-N
, N-dipropylamino (meth)acrylate, 2-N
, t-butylaminoethyl (meth)acrylate, 2-
(4-morpholino)-ethyl (meth)acrylate, 2
-vinylpyridine, 4-vinylpyridine, aminostyrene, etc.

In addition, the anionic group-containing vinyl monomers include carboxyl groups or their salts such as (meth)acrylic acid, itaconic acid, phlotic acid, maleic acid, fumaric acid, etc.
monomer, styrenesulfonic acid, vinyltoluenesulfonic acid, vinylethylbenzenesulfonic acid, isopropenylbenzenesulfonic acid, 2-chlorostyrenesulfonic acid, 2-methyl-4-chlorostyrenesulfonic acid, vinyloxy/benzenesulfonic acid, vinyl Sulfonic acid,(
Monomers containing sulfonic acid groups or their salts, such as meth)allylsulfonic acid, sulfoethyl (meth)acrylic acid, sulfopropyl ester of (meth)acrylic acid, and 2-acrylamido-2-methylpropanesulfonic acid; ) acrylate, azidophosphoxypropyl (meth)acrylate, 3-chloro-2-azidophosphoxy7propyl methacrylate, bis(meth)acryloxyethyl phosphate, vinyl phosphate, and other monomers containing a phosphoric acid group or a salt thereof.

In order to achieve the objective [j] of the present invention, a combination of an anionic group-containing polyester and a cationic group-containing vinyl monomer is more desirable. In addition, there is no problem in appropriately using known nonionic monomers.

There are no particular restrictions on the polymerization initiator used in the F-combination of vinyl monomers, such as base/soil peroxide, acetyl peroxide, etc. .2'-Azobis(2,4-trimethylvaleronitrile) and other ano compounds, inorganic peroxides such as persate, hydrogen peroxide, permanganate A, acetic acid containing the inorganic peroxide, 1T1 'Fururic acid salt, metafururic acid salt,
Examples include water-soluble redox initiators with reducing agents such as hydroflusulfates, thiosulfates, iron salts, and oxalic acid.From a safety standpoint, water-soluble redox initiators are recommended. preferable. The amount of polymerization initiator used is generally within the range of 0.1 to 3% based on the vinyl monomer.

Although it is difficult to define the polymerization temperature unambiguously, the polyester resin powder r dispersed in the aqueous medium is allowed to coalesce and grow into a spherical shape as the vinyl monomer polymerizes, and the glass transition temperature (Tg) of the polyester is It is preferable to adopt the temperature conditions listed below. Under conditions below this temperature, irregularly shaped particles are likely to be formed. By using a polyester solvent and iiJ plasticity in combination, the apparent glass transition point (or minimum film formation temperature) of the polyester can be lowered and polymerization can be carried out at 1" below this temperature.Such a solvent There is no limitation on the type of plasticity, and it is appropriately selected from known types depending on the type of polyester as long as it does not inhibit polymerization.

Other polymerization conditions may be carried out according to conventional methods, or the first step may be a step in which a vinyl monomer is charged in advance into an aqueous dispersion of polyester fine particles, and then a polymerization initiator is added to aT', rapid coalescence or aggregation of the polyester fine particles, etc. This is preferable because there are no problems.

The obtained aqueous dispersion of polyester resin particles is taken out as a dry powder by a conventional method such as filtration, freeze drying, spray drying or the like.

Thus, the toner of the present invention is a substantially spherical particle with a ratio of the major axis to the minor axis of 0.7 or more, and the diameter is in the range of 0.5D to 2D, where D is the downward particle diameter. It is possible to industrially produce polyester resin particles having a relatively sharp distribution that accounts for more than 70% of the total number of particles with a particle size within 3 degrees. The points are 1) 0°C or higher and 1; If the glass transition point is lower than this, there is a tendency to agglomerate during handling or storage, which may cause storage stability problems.

The softening point of the polyester resin in the present invention is 80 to 1
The range is 50°C. Toners in which the softening temperature of the resin is kept lower than this tend to aggregate during handling or storage, and fluidity may deteriorate significantly, especially during long-term storage. If it is at or above the softening point, fixing performance will be impaired. Further, since it is necessary to heat the fixing roll to a high temperature, the material of the fixing roll and the material of the base material to be copied are limited.

One of the features of the Shinr photographic toner of the present invention is that it contains a polyester resin "four-colored with pigments" as one component.

Pigments include anorki pigments, rhodamine pigments,
Quinacridone pigments, etc. can be used.

More specifically, oil blue, alkaline blue, phthalon anine blue, phthalon anine green 7, Spiri, Doppler, Ri, Anili/Bra, Ri, oil violet, pen 7 nono yellow, methyl orange, friliant carmine, fast red, crystal. It is difficult to use pigments such as violet.

Further, when obtaining a black toner, carbon black or the like may be used together.

In the electrophotographic toner of the present invention, a charge control agent may be used to provide stable charge.

Examples of charge control agents that positively charge the toner through friction with carrier particles include titanates such as Ca5Ba, carbonates, alkoxylated amines, polyamide resins exclusively for nylon, phthalonanine blue, quinacridonelend, Azo metal complex green, a pigment with positive zeta potential represented by Yoshi,
Examples include azine compounds, stearic acid-modified anone compounds, olei/acid-modified anone compounds, anone pigments such as Nigro/N, and quaternary ammonium salt compounds.

The charge control agent that imparts an electric charge to the toner by friction with the carrier (carrier) may be, for example, carbon black, halogenated phthalocyanine,
Examples include pigments with negative zeta potential such as flavanstone yellow and perylene red, and trimetallic compounds such as copper, zinc, lead, and iron.

In the toner of the present invention, a fluidity modifier such as fine alumina particles and/or fine particles of lyca may be added.

The amount added is not particularly limited, but from the viewpoint of imparting appropriate fluidity, it is preferably 0.00 to the toner.
It is about 0.01 to 5% by weight, more preferably about 0.1 to 2% by weight.

Toner used without being mixed with carrier particles (carrier): - In the case of a component-based developer, the toner must have magnetism. In such a case, iron, cobalt, nickel, an alloy mainly composed of these, or an oxide exclusively for ferrite may be included, if necessary.

The method of treating particles with the four coloring agents, charge control agents, fluidity modifiers, etc. described above is not particularly limited, and any known and existing treatment method may be used. These may be dispersed in, for example, particles, may be coated on particles, or may be implanted onto particle surfaces by, for example, a dry process such as mechanofusion.

The polyester resin used in the toner of the present invention exhibits good fixing properties because it does not cause fusion or aggregation at room temperature, and its viscosity quickly decreases during fixing. Furthermore, since it exhibits a sharp particle size distribution, it has excellent image reproducibility, especially fine line reproducibility.

(Example) The present invention will be described in further detail with reference to Examples below, but the present invention is not limited to these in any way. In addition, physical properties of resins and the like in Examples and Comparative Examples were measured by the following methods.

・Melting point, glass transition point W,
? Measurement was performed at a Q rate of 1 °C/min.

・Softening point Measured according to JIS K2351.

・Number average molecular microscopy (steam IL method) Measurement was performed using a molecular bottle measuring device (manufactured by Nippon Seisakusho).

The diameter was measured using an automatic particle size distribution analyzer model CAPA700 manufactured by Shimabara Seisakusho.

・Sphericity Measure the major axis and minor axis from the image of the projected sphere measured by an optical microscope, and measure the sphericity by the ratio of the minor axis to the major axis. If it is 1.0, it is a true sphere, I, O or more. It was determined that the ball was deformed.

[Example 1] In an autoclave equipped with a thermometer and a stirrer, 4 parts of dimethyl terephthalate, 94.1 ff of dimethyl isophthalate, 95 tons of dimethyl isophthalate, and 8 parts of ethylene glycol were added. 1 part by weight, neopentyl glycol 8
0 [31 parts, and tetraphthoxy titanate 0
．． 1 part of It was charged and heated at 120 to 230°C for 120 minutes to perform transesterification reaction. Then 5-sodium sulfoisophthalic acid 8,'
After adding 1 part of t t , the reaction was continued at 220 to 230°C for 60 minutes, and the temperature was further raised to 250°C, and the reaction was continued for 60 minutes at a system pressure of 1 to 10+nHg. As a result, the copolymerized polyester (A1) Obtained.

The molecular weight of the obtained copolymerized polyester (A1) is 270
0, sulfonic acid metal base is 1) 8 equivalents/1000000
It was g. The amount of sulfonic acid metal base was determined by measuring 1 degree of sulfur in the copolymerized polyester resin. In addition, the composition of the copolymerized polyester (A1) was determined by NMR analysis to include, as acid components, 48.5-% terephthalic acid, 48.0-% isophthalic acid, 5-sodium,
Sulfoisophthalic acid was 2.5 J%, and alcohol components were: ethylene glycol e+,o[lQ%] neopentyl glycol 39.0%.

15) Coarsely pulverized copolymerized polyester (A1), toozi part, azo yellow pigment, and 5 market parts are mixed in a ball mill, ground, and then melted and mixed in a roll mill to obtain blue copolymerized polyester (AIY). I got it.

1) After dissolving 34 parts by weight of the obtained copolymerized polyester (AIY) and 10 parts by weight of butyl cellosolve at 0°C in a four-necked 1-liter separable flask equipped with a thermometer, condenser, and stirring blade. , water at 80°C was added with 56 parts of heavy acid to form an aqueous dispersion of colored copolymerized polyester (B
I Y) was obtained.

Four [1 of 1] equipped with a thermometer, condenser, and stirring blade
Litho) In a separable flask, add 834 parts of colored copolymerized polyester aqueous dispersion (BIY) and 35 parts of deionized water.
and dimethylaminoethyl methacrylate)
A 5.6 ft. portion was added and the temperature was raised to 70°C. Next, 100 ton i parts of an aqueous solution containing 0.2 parts by weight of am/monium peroxide was added dropwise over 40 minutes, and then 70 parts for another 60 minutes.
The reaction was continued while being maintained at °C. As a result, the submicron-order particle size copolymer present in the colored copolymerized polyester aqueous dispersion grew into particles, and ・V average particle size was 8.7.
/jJ, polyester resin particles (CIY) with a 92% occupancy (number) of particles having a particle size ranging from 0.5D to 2D, where D is the diameter, were obtained. Then cooled, filtered,
It was washed and dried in vacuum to obtain a yellow toner (DIY).

Similarly, a magenta toner (DIM) and a cyan toner (DIG) were obtained using a rhodamine-based red pigment and a phthalocyanine-based blue pigment.

5 parts by weight of each of the obtained colored toners were mixed with 95 parts by weight of a carrier (spherical reduced iron powder with an average particle size of 80 units) to obtain a two-component electrophotographic developer. The charging spear of the toner after mixing with the carrier was (DIY) -81 μC/g (DIM) -78 μC/g (DIC) -71 μC/g. Using these developers, 5,000 copies were continuously made on paper using an electrophotographic Kh type color copying machine using an amorphous/recon photoreceptor. The resulting copy was free from fog and fading, and showed a clear and good image.

Further, no particular problems were observed in the humidity dependence of charging properties, flow properties, insulation properties, etc., as well as ankle properties, sharp melt properties, off-setting/separation resistance, etc.

[Comparative Example 1] Copolymerized polyester (At) 9 obtained in Example 1
0 parts by weight, an azo yellow pigment, a rhodamine red pigment,
101 parts of phthalocyanine-based blue pigment were premixed in a ball mill, melted and mixed in a 10-luminium mill, pulverized and divided into spheres in a pulverizer, and colored toner (D2Y) (D2M) with a uniform particle size of 14 pj was prepared. ) (D2C) was obtained.

5 parts by weight of each of the obtained colored toners were mixed with 95 parts by weight of carrier (spherical reduced iron powder with an average particle size of 80 mm) in the same manner as in the example to obtain a two-component electrophotographic developer. The charge values of the toner after mixing with the carrier were (D2Y) -41 μC/g (02M) -35 μC/g (D2C) -32 μC/g. Using these developers in the same manner as in Example 1, 5,000 copies were continuously made on paper using an electrophotographic color copying machine using amorphous silicon as a photoreceptor. The resulting copy had many scratches in the fine line areas, and a good image could not be obtained.

[Example 2] In an autoclave equipped with a thermometer and a stirrer, 94 parts by weight of dimethyl terephthalate, 95 parts by weight of dimethyl isophthalate, 80 parts by weight of ethylene glycol,
120 parts by weight of neopentyl glycol and 0.1 parts by weight of tetraphthoxy titanate
The transesterification reaction was carried out by heating at ~230°C for 120 min.
It was f. Then, 5-natori Umsurunei 17 taru
Add 6.71H parts of acid and heat to 220-230°C
Continue the reaction for 60 minutes at 250"C (7
After M, the reaction was continued for 60 minutes at a system pressure of 1 to 10 mmHg, resulting in a copolymerized polyester (A3).

The molecular density of the obtained copolymerized polyester (A3) is 270
0, sulfo/acid metal base is 1) 8 equivalents/1000000
It was g. The amount of sulfonic acid metal base was determined by measuring the sulfur concentration in the copolyester. In addition, as a result of NMR analysis, the composition of the copolymerized polyester (A3) was found to be 49.51I terephthalic acid [lQ%] as an acid component.
Isophthalic acid 50.0,0% 5-sodium sulfoisophthalic acid 2.5. (1%, alcohol component: ethylene glycol 53.0%, neopentyl glycol 47.0mC1%.

Four [1 of 1] equipped with a thermometer, condenser, and stirring blade
1) In a separable flask, dissolve 34 parts of polymerized polyester (A3) and 10 parts of butyl cellosolve at 0°C, and then
56 parts of water of 'c was added to obtain a copolymerized polyester aqueous dispersion (B3).

Into four 1-liter separable flasks equipped with a thermometer, condenser, and stirring blade, add JJ [polyester aqueous dispersion (B3) 83441) M, deionized water 35
parts by weight and 5.6 parts by weight of dimethylaminoethyl methacrylate were added, and the temperature was raised to 70°C. Next, 100 parts by weight of an aqueous solution containing 0.2 parts by weight of ammonium persulfate was added to 4 parts by weight.
After dropping for 0 minutes, the reaction was continued in a state where the temperature was kept at 70° C. for an additional 60 minutes. As a result, submicron-order particles Y present in the copolymerized polyester aqueous dispersion were found.
The copolymer has a particle size of 92%, with an average particle size of 5.6 and a particle size in the range of 0.5D to 2D, where D is the diameter. Resin particles (
C3) was obtained.

1) Polyester resin particles f'-95Itlu
After mixing part and ano-based color pigment, and 5 parts of small value,
Both materials were fused using the Mechanofu/J// stem to obtain a copolyester resin tQf-, the surface of which was coated with an Ab type b' monochromatic pigment, that is, an electrophotographic toner (A3Y).

Similarly, a magenta toner (D3M) and an ant toner (D 3 C) were obtained using a rogue-gummy red pigment, a phthalonanine-based pigment, and a one-color pigment.

5 parts by weight of each of the obtained blue toners was added to a carrier (・V
Mix with 95 parts of spherical reduced iron powder with an average particle size of 80,
A component-based electrophotographic developer was obtained. The charge amount of the toner after mixing on the carrier is (1) 3 Y ) -92 μC/g (1) 3 M)
-85μC/g (D3C) -79μC/g. Using these developers, 5,000 sheets of paper were continuously copied using an electrophotographic color copying machine using an amorphous/recon photoreceptor. The resulting copy showed a clear and good image with no fogging or fading.

Also, the humidity dependence of charging characteristics, flow characteristics, insulation f'1, etc., as well as fixing properties, yarn melting properties, and offset resistance.

No particular problems were observed in terms of stability, etc.

(Effects of the Invention) As mentioned above, the toner according to the present invention has humidity dependence such as charging characteristics, flow characteristics, and insulation properties, as well as fixing properties,
It has excellent sharp melt properties, anti-offset properties, etc., and particularly excellent reproducibility of fine line images.

Claims (2)

[Claims] (1) Softening point is 80-150℃, glass transition point is 40℃
It is characterized by containing the resin (A) whose main component is the above polyester as a base material and having a number average of 70% or more of particles with a sphericity (ratio of major axis to minor axis) of 0.7 or more. Toner for electrophotography. (2) The toner for electrophotography according to claim (1), which is colored with a pigment.