JP2000019771A - Dry toner and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent environmental stability and to prevent the pollution of a toner carrier and the like by containing a specific quantity of a compound selected from a group comprising specific aromatic oxycarboxylic acid and specific azo dye, and having specific circularity distribution. SOLUTION: Dry toner contains binding resin, a coloring agent, wax and one more kinds of compounds selected from a group comprising aromatic oxycarboxylic acid expressed by a formula I and azo dye expressed by a formula II. The total content of the compound is 0.01-3 wt.% of the weight of the toner, and material with a fusing point of 35-80 deg.C in a styrene monomer is contained as wax as 0.5-10 wt.% of the weight of the binding resin. The average circularity of the toner is 0.95-0.995. The toner contains grains less than 0.95 in circularity at 1-30 number %, and the peak of number frequency (%) exists in circularity of 0.95 or more. In the formula II, Ar represents aryl group, X and Y independently indicate -O-, -CO-, -NH-, or the like and D and F independently indicate -H, -OH, -Na, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry toner (hereinafter referred to as "toner") used for a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, and the like, It relates to a manufacturing method.

[0002]

2. Description of the Related Art Various methods of electrophotography have been proposed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748.

As a method of developing an electrostatic image, there are a dry development method and a wet development method. Dry development is divided into a method using a two-component developer and a method using a one-component developer.

[0004] The toner applied to the dry development method is generally a fine particle containing a binder resin, a colorant and a wax as a main component, and usually has a particle diameter in the range of 8 to 30 µm. As a method for producing the toner particles, a binder resin, a coloring agent such as a dye / pigment and / or a magnetic substance, a wax and the like are melt-kneaded, the kneaded material is cooled, and the cooled kneaded material is pulverized.
There is a method of classifying a pulverized product to generate toner particles.

[0005] Toner must have a positive or negative charge, depending on the polarity of the electrostatic image to be developed. In order to cause the toner to retain an electric charge, the frictional charging property of a resin as a component of the toner can be used, but in this case, the charging property of the toner is generally low. In order to impart desired triboelectricity to a toner, a charge control agent is added to the toner.

In general, a toner containing a charge control agent sometimes shows a relatively high triboelectric charge, but the triboelectric charge decreases under high humidity. On the other hand, under low humidity, the charging speed of the toner decreases.

One of the causes is considered to be the absorption and desorption of water near the charge control agent. The amount of water adsorbed on the charge control agent increases under high humidity, and the triboelectric charge decreases. It is considered that since the amount of adsorbed water in the control agent decreases, the resistance increases and the charging speed decreases.

Therefore, for example, JP-A-4-34763 and JP-A-4-170557 propose toners containing an aromatic oxycarboxylic acid and an azo dye, respectively. It is expected that the aromatic oxycarboxylic acid and / or azo dye controls the adsorption of moisture to the charge control agent, thereby suppressing a decrease in the triboelectric charge amount and the charging speed. However, according to the study of the present inventors, the inclusion of these compounds improves the triboelectric charge amount and the charging speed under specific prescriptions and conditions, but easily adheres to a toner carrier such as a sleeve. However, there is a problem that the toner carrier is contaminated when copying is continued.

Another cause is that since the circularity of the toner is not controlled, when an external additive is used, it is difficult for the external additive to be uniformly added to the toner surface, and the degree of aggregation and the toner particle It is considered that a change in the contact state between the toner and the external additive causes a reduction in the triboelectric charge amount and the charging speed.

On the other hand, in recent years, with the demand for higher image quality and higher resolution of electrophotographic images, a method for producing a toner by a polymerization method in an aqueous medium for the purpose of reducing the particle size and function of the toner. Has been proposed. These are, for example,
JP-A-6-10231, JP-B-51-14895, JP-A-53-17735, JP-A-53-17
736 and JP-A-53-17737.

In the above-described method, substances to be included in the toner, such as a colorant such as a binder resin, a dye and a pigment, for example, a magnetic substance, carbon black, a charge control agent, and a release agent such as wax and silicone oil are used. If necessary, dissolve or disperse in a polymerizable monomer together with a polymerization initiator or a dispersant to form a polymerizable composition, and disperse in a water-based continuous phase containing a dispersion stabilizer using a dispersing device to obtain fine particles. Of the desired particle size by polymerizing and solidifying this dispersion,
This is to obtain toner particles having a composition.

Since the above-mentioned method does not include steps such as kneading and pulverization, effects such as energy saving, improvement in process yield, and cost reduction are expected.

However, in the polymerization method in an aqueous medium as described above, a hydrophilic compound having a large contact area with the aqueous medium and containing a large amount of a polar group which has been conventionally internally added to the toner particles can be used. In some cases, it is difficult to effectively add the toner particles internally without dissolving them in the medium.

In particular, the aforementioned aromatic oxycarboxylic acids and / or
Or, when the toner particles containing the azo dye are produced by a polymerization method in an aqueous medium, the dissolution is remarkable, and it is difficult to encapsulate these compounds in the toner particles. Also, there is a problem in that the toner tends to precipitate on the particle surface due to its high polarity, and contaminates the toner carrier.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dry toner which has solved the above-mentioned problems and a method for producing the same.

That is, an object of the present invention is to provide a dry toner which is excellent in environmental stability and does not contaminate a toner carrier and the like, and a method for producing the same.

[0017]

According to the present invention, at least (i) a binder resin, (ii) a colorant, (iii) a wax and (iv) an aromatic oxycarboxylic acid represented by the following general formula (1): A dry toner containing at least one compound selected from the group consisting of azo dyes represented by the following general formula (2), wherein the total content of the compounds is 0.01 to 3 based on the weight of the toner. % Of a wax having a melting point of 35 to 8 in a styrene monomer.
The substance at 0 ° C. is 0.5 to 1 based on the weight of the binder resin.
1 to 30% by number of particles containing 0% by weight and having an average circularity of 0.950 to 0.995 and a circularity of less than 0.950 in the circularity distribution of the toner.
The present invention relates to a dry toner, wherein the peak of the number frequency (%) is present at a circularity of 0.950 or more.

[0018]

Embedded image

[0019]

Embedded image [Wherein, Ar represents an aryl group, which may have a substituent, and X and Y represent -O-, -CO-, -NH
-Or -NR- (R represents an alkyl group having 1 to 4 carbon atoms), and D and F represent -H, -OH, -Na or-.
K is shown. ]

Further, the present invention provides (I) at least a polymerizable monomer, a colorant, a polymerization initiator, a wax having a melting point in the range of 35 to 80 ° C. in styrene, and the above-mentioned general formula (1) ) And / or the azo dye represented by the general formula (2) at 35 to 90 ° C.
Preparing a monomer composition by mixing in a temperature range of,
(II) a step of granulating the monomer composition in an aqueous medium having a pH in the range of 3 to 7, and (III) a step of mixing the polymerizable monomer granulated in the aqueous medium with 35 to 35. Polymerization in a temperature range of 90 ° C.

[0021]

DETAILED DESCRIPTION OF THE INVENTION As a result of intensive studies, the present inventor has found that the above-mentioned structure solves the above-mentioned problem.

The circularity in the present invention is used as a simple method for quantitatively expressing the shape of a particle.
In the present invention, a flow particle image analyzer FP manufactured by Toa Medical Electronics Co., Ltd.
The measurement is performed using IA-1000, and the value obtained by the following method is defined as circularity.

As a specific measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impurity solids and the like have been removed in advance. And 0.1 to 0.5 g of a measurement sample are further added. The suspension in which the sample was dispersed was subjected to dispersion treatment for 1 to 3 minutes with an ultrasonic disperser, and the dispersion concentration was adjusted to 3
The shape and the particle size of the toner are measured by the above-mentioned device at 000 to 10000 particles / μl. The circularity is obtained by the following equation.

Circularity a = L ₀ / L (L ₀ : circumference of a circle having the same projected area as the particle image, L:
Perimeter of projected image of particle)

The average circularity is an average value obtained by dividing the total circularity obtained as described above by the number of particles.

The circularity in the present invention is an index of the degree of unevenness of the toner, and is 1.0% when the toner is perfectly spherical.
And the degree of circularity becomes smaller as the surface shape becomes more complicated.

Conventionally, proposals have been made for controlling the toner shape similar to the circularity of the present invention, but no proposal has been made for controlling the distribution of the toner shape.

In the present invention, the average circularity in the circularity distribution is 0.950 to 0.995, and 1 to 30% by number of particles having a circularity of less than 0.950 are contained. %) Preferably exists at a circularity of 0.950 or more.

When the average circularity of the toner is less than 0.950, the above-mentioned wax, aromatic oxycarboxylic acid and / or azo dye tends to locally precipitate on the surface of the toner particles at the uneven portions on the surface of the toner particles. This causes problems such as reduced durability and contamination of the toner carrier.
If it exceeds 0.995, poor cleaning tends to occur.

When the content of the particles having a circularity of less than 0.950 is less than 1% by number, poor cleaning is liable to occur. The wax, the aromatic oxycarboxylic acid and / or the azo dye are likely to locally precipitate on the surface of the toner particles, causing a problem that the durability is reduced and the toner carrier is contaminated.

In general, a wax is contained in a toner for the purpose of improving fixability and releasability, but the present inventors have conducted intensive studies and as a result, when a wax having specific physical properties is used under specific conditions. In addition, they have found that it is possible to improve the effect of the addition of the above-mentioned aromatic oxycarboxylic acid and / or azo dye, and to prevent leakage to the outside. This is because the above-mentioned aromatic oxycarboxylic acid and / or
Alternatively, it is considered that a hydroxyl group or a carboxyl group contained in the azo dye and a polar group contained in the wax are hydrogen-bonded, and moderate molecular chain motion is maintained while promoting intramolecular polarization. .

The physical properties and content of the wax used in the present invention are such that when the above-mentioned aromatic oxycarboxylic acid and / or azo dye is used in an amount of 0.01 to 3% by weight, the melting point in styrene is 35 to 35%. A wax in the range of 80 ° C., and the content of the wax is 0.5 to 1 with respect to the binder resin.
0% by weight.

In the present invention, the melting point of the wax in styrene is different from the so-called melting point, and indicates a temperature at which the wax can be uniformly mixed with styrene. For example, there is a wax that cannot be uniformly mixed with styrene even if its melting point is 50 ° C. Conversely, even if the melting point is 100 ° C., it may be possible to uniformly mix with styrene at 80 ° C. Specifically, it indicates the lowest temperature in the temperature range obtained as a result of measurement by the method described below.

After sufficiently pulverizing the wax, a 300 cc flask equipped with a reflux condenser and a mechanical stirrer was placed in a 300 cc flask.
When 5 g of wax is added to 100 g of styrene monomer, and the mixture is stirred at a rotation speed of 200 rpm for 30 minutes in an oil bath maintained at a predetermined temperature of 5 ° C., substantially solid content is visually confirmed. It indicates the lowest temperature value in a temperature range where the temperature cannot be maintained (this temperature range is referred to as a dissolution temperature range in styrene in the present invention).

In the case of a wax having a melting point of less than 35 ° C. in styrene, the wax is softened by a trace amount of monomer remaining in the toner under high temperature and high humidity, and the above-mentioned aromatic oxycarboxylic acid and / or azo dye leaks. And the toner carrier is contaminated.
Further, a wax having a melting point in styrene exceeding 80 ° C. has a small interaction with an aromatic oxycarboxylic acid or an azo dye, so that an effect of improving these properties cannot be obtained.
Further, there is a problem that the melt viscosity is large and the fixability is deteriorated.

As the wax used in the present invention, a known wax satisfying the above-mentioned conditions can be used. More preferably, the wax is more specifically a polar wax, and the ethylene unit (—CH ₂₎ contained in the wax is used. -) and the abundance ratio of the ester bond _{(-OCO-) ([-CH 2 -} ] / [-
A polar wax having an OCO-]) in the range of 5 to 50 is preferably used. ([-CH _2- ] / [-OCO
When the value of-]) does not exceed 5, the polarity of the wax is too large, so that the aromatic oxycarboxylic acid and / or
Alternatively, since the compound has a strong interaction with a compound such as an azo dye, the effect of suppressing contamination of the toner carrier is exhibited, but the molecular chain motion of the compound is suppressed, and the effect of including the compound is reduced. There are cases. Also,
When the value of ([—CH ₂ —] / [— OCO—]) exceeds 50, the interaction between the compound and the wax is small, so that the number of hydrogen bonding points with the compound is small, and the intramolecular In some cases, the effect of promoting polarization may not be obtained so much. In the present invention, ([-CH _2- ] / [-OCO
The value of-]) is preferably determined by the following method.

Using 200 ml of tetrahydrofuran as a solvent, 10 g of the toner is subjected to Soxhlet extraction for 12 hours, and the solvent is removed from the soluble components in tetrahydrofuran using an evaporator. 100 ml of chloroform are added to the residue and stirred for 12 hours. The insoluble matter was recovered by filtration, dissolved in deuterated tetrahydrofuran, using EX400 of JEOL Co. 400MHz, perform C ¹³ -NMR measurement, calculated from the integral value of the peak.

The aromatic oxycarboxylic acid used in the present invention is a compound represented by the following general formula (1).

[0039]

Embedded image

The aromatic oxycarboxylic acid used in the present invention is preferably a monoalkyl or dialkyl aromatic oxycarboxylic acid. This is because, in the case of a monoalkyl or dialkyl aromatic oxycarboxylic acid, the negative charge density of oxygen of the carboxyl group is small due to the resonance structure, so that the metal compound has a high negative charge ability, and the coexisting monoalkyl or dialkyl substituted aromatic Since oxycarboxylic acid has a three-dimensionally large structure, it is conceivable that water molecules are easily blocked.

More preferable compounds of the aromatic oxycarboxylic acid used in the present invention include salicylic acid, alkyl salicylic acid, iron complexes of monoazo dyes, and hydroxynaphthoic acid. As alkyl salicylic acid, tert-butylsalicylic acid, 5-t
tert-Butylsalicylic acid is mentioned, and the iron complex of a monoazo dye is di-tert-butylsalicylic acid. Particularly preferred is di-tert-butylsalicylic acid.

The azo dye used in the present invention is a compound represented by the following general formula (2).

[0043]

Embedded image [Wherein, Ar represents an aryl group, which may have a substituent, and X and Y represent -O-, -CO-, -NH
-Or -NR- (R represents an alkyl group having 1 to 4 carbon atoms), and D and F represent -H, -OH, -Na or-.
K is shown. ]

As the azo dye used in the present invention, a preferable compound is a monoazo dye having two or more hydroxy groups. More specifically, a compound represented by the following general formula (3) or (4) is preferable.

[0045]

Embedded image [Wherein R ₁ and R ₂ represent hydrogen, halogen, nitro group, or alkyl group, and R ₃ and R ₄ represent hydrogen, halogen, nitro group, carboxyl group, hydroxyl group, alkyl group, or halogen or nitro group. It represents a benzamide group or a benzsulfoamide group which may be possessed. ]

In the present invention, the amount of the aromatic oxycarboxylic acid and / or azo dye used is preferably in the range of 0.01 to 3 parts by weight based on 100 parts by weight of the binder resin. When the amount is less than 0.01 part by weight, the effect of adding the aromatic oxycarboxylic acid and / or the azo dye is small. Three
When the amount is more than 10 parts by weight, the charging rate under low humidity is low, and at the time of fixing by a heating and pressing roller, an aromatic layer such as a silicone rubber layer on the surface of the heating roller is coated with an aromatic oxycarboxylic acid and / or an azo dye. Easily contaminated, the contaminated elastic layer can be easily degraded and susceptible to damage.

In the present invention, the amounts of the aromatic oxycarboxylic acid and / or azo dye, the wax and the binder resin are preferably added in a weight ratio of (0.01-3) / (1-2).
0) / 100, and more preferably (0.1-1) /
(1-10) / 100.

In the present invention, the toner particles have a structure in which an A phase having a binder resin as a main component and a B phase having a wax as a main component are separated from each other. It is preferable that the B phase does not exist near the surface up to a depth of 05 times.

The wax described above interacts with a compound such as an aromatic oxycarboxylic acid and / or an azo dye, and by controlling the circularity of the toner, the compound is prevented from leaking out. Although it is possible to prevent a decrease in the triboelectric charge amount, it is considered that the compound interacts with the wax and is relatively present in the B phase. For this reason, since the above-mentioned B phase does not exist on the toner surface, the effect of preventing leakage of the compound is further improved, and the content of the compound in the toner is maintained even during continuous printing. It is considered that the effect of suppressing the decrease in the triboelectric charge amount under high temperature and high humidity is maintained, and the effect of preventing the toner carrier from being stained is maintained.

The toner according to the present invention preferably contains an inorganic fine powder having an average particle diameter in the range of 10 to 500 nm in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the toner particles. Of cohesion is 1 to 30%
It is better to be in the range. By using an inorganic fine powder having a controlled particle size, when a compound such as an aromatic oxycarboxylic acid and / or an azo dye is deposited near the toner surface, the compound interacts with the compound and causes the moisture of the toner particles to be transferred to the toner particles. This is because the adsorption is more remarkably controlled, and the effect of suppressing the decrease in the triboelectric charge amount under high temperature and high humidity and the decrease in the charging speed under low temperature and low humidity increases. Further, the interaction between the compound and the inorganic fine powder increases the effect of the compound to prevent contamination of the toner itself.
Further, by controlling the degree of aggregation of the toner, the contact state between the toner particles and the inorganic fine powder is controlled, and the above-described effect is maintained even in continuous copying.

In the present invention, the average particle diameter of the inorganic fine powder is preferably from 10 to 500 nm, more preferably from 10 to 200 nm. When the thickness does not exceed 10 nm, the degree of aggregation of the toner may change with time because the inorganic fine powder is embedded in the surface of the toner particles during continuous copying. In addition, since the surface area of the inorganic fine powder is large, when a compound such as an aromatic oxycarboxylic acid and / or an azo dye is present on the surface of the toner particles, the interaction with the compound is large, and the compound absorbs and desorbs water. Control effect becomes smaller. Further, in the range exceeding 500 nm, since the surface area of the inorganic fine powder becomes small,
Interaction sites with a compound such as an aromatic oxycarboxylic acid and / or an azo dye are saturated, and the effect of preventing contamination of the toner carrier is reduced.

In the present invention, the average particle diameter of the inorganic fine powder is determined by measuring the toner with a scanning electron microscope (FE-SEM S-80).
0 Hitachi, Ltd.) It can be obtained from the photograph. 10
A photograph was taken at a magnification of 000 times, and the image was further enlarged 400 times by a color copier (manufactured by CLC-800 Canon). From the image, the maximum length of one inorganic fine powder and the length in the vertical direction were determined. The average value is defined as the particle size of the inorganic fine powder. The measurement is performed until the number of the measured inorganic fine powder reaches 300, and the average value is defined as the average particle diameter.

The amount of the inorganic fine powder is in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the toner particles. If the amount is less than 0.5 part by weight, it is similarly difficult to control the degree of aggregation of the toner of the present invention. If the amount exceeds 5% by weight, the released inorganic fine powder contaminates the toner carrier. There is.

Further, the degree of aggregation of the toner of the present invention is preferably in the range of 1 to 30%, and more preferably in the range of 5 to 20%. It is considered that the fluidity of less than 1% is achieved by constantly changing the contact state between the inorganic fine powder and the toner particles. Supplied to the acid and / or azo dye, the water absorption of the aromatic oxycarboxylic acid and / or azo dye becomes saturated. When the content exceeds 30%, the change in the contact state between the inorganic fine powder and the toner particles is too small, so that when a compound such as an aromatic oxycarboxylic acid and / or an azo dye is present on the surface of the toner particles, the compound may not be in contact with the compound. Interaction site becomes saturated.

In the present invention, the degree of aggregation of the toner is measured by the following method.

Using a vibrating sieve of a powder tester (manufactured by Hosokawa Micron Co., Ltd.), 400 mesh, 200 me
The sieves are set in the order of sh and 100 mesh. 5 g of the toner is gently placed on the overlapped sieve, and then vibrated for 15 seconds. Thereafter, the weight of the toner remaining on each sieve is measured, and the degree of aggregation is determined by the following equation.

[0057]

(Equation 1)

As the inorganic fine powder used in the present invention, specifically, for example, metal oxides (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride and the like are suitably used. These are more preferably subjected to a hydrophobic treatment. As the abrasive, a metal oxide (such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide) is preferably used.

In the present invention, the number average particle diameter (D
1) is obtained in the same manner as the above-described method for obtaining the circularity. In the present invention, the number average particle diameter of the toner is preferably in the range of 2 to 8 μm. When the thickness exceeds 8 μm, the effect of the encapsulated aromatic oxycarboxylic acid and / or azo dye may be reduced. Further, if the thickness does not exceed 2 μm, it may be difficult to encapsulate the aromatic oxycarboxylic acid and / or the azo dye.

The binder resin of the toner in the present invention includes polystyrene; styrene-substituted homopolymers such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer and styrene-vinyltoluene copolymer. Polymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polysalt Vinyl, phenolic resin, naturally modified phenolic resin, naturally modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene Resin, coumarone indene resin, petroleum resin and the like.

[0061] Crosslinked styrenic copolymers and crosslinked polyester resins are also preferred binder resins.

As comonomers for the styrene monomer of the styrene copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, Monocarboxylic acid having a double bond such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, maleic acid Dicarboxylic acids having a double bond such as methyl acrylate and dimethyl maleate and their substituted products; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene such as ethylene, propylene and butylene Olefins; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ether such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

As the crosslinking agent, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; Divinyl ether,
Divinyl compounds such as divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

When the binder resin is a styrene-acrylic copolymer, the molecular weight distribution is determined by gel permeation chromatography (GPC) of THF-soluble components, and the molecular weight is 3,000 to 5,000.
And at least one peak in the 10,000
A binder resin in which 10,000 or less components are 50 to 90% is preferable.

The black colorant used in the present invention includes:
Carbon black, a magnetic substance, and a substance toned to black using a yellow / magenta / cyan colorant shown below are used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture, or can be used in the form of a solid solution.

The amount of the colorant added is preferably 40 to 150 parts by weight per 100 parts by weight of the binder resin when a magnetic material is used, and the binder resin is added when another colorant is used. It is preferable to add 5 to 20 parts by weight per 100 parts by weight.

The toner of the present invention may be a magnetic toner containing a magnetic material. In this case, the magnetic material can also serve as a colorant. Examples of the magnetic substance that can be used in the toner of the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum of these metals;
Examples include alloys of metals such as cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The magnetic material used in the present invention is more preferably a surface-modified magnetic material. In the case of using a polymerization method, it is preferable to use a surface-modifying agent that does not inhibit polymerization and that has been subjected to a hydrophobic treatment. As such a surface modifier,
For example, a silane coupling agent, a titanium coupling agent and the like can be mentioned.

These magnetic materials have an average particle size of 1 μm or less,
Preferably, the thickness is 0.1 to 0.5 μm.

The magnetic material has a magnetic characteristic of 10 to 300 oersteds of coercive force (Hc), 50 to 200 emu / g of saturation magnetization (σs), and 2 to 20 emu / g of residual magnetization (σr) when applied with 10K sled. preferable.

In order to stabilize the frictional charging characteristics of the toner, a charge control agent may be contained. In this case, it is preferable to use a charge control agent which has a high toner charging speed and can stably maintain a constant charge amount. When a polymerization method is used, a charge control agent having no polymerization inhibition is particularly preferable. Specifically, examples of the negative control agent include salicylic acid, alkyl salicylic acid, iron compounds of monoazo dyes, metal compounds such as naphthoic acid and dicarboxylic acid; sulfonic acids, high molecular weight compounds having carboxylic acid in the side chain, and boron compounds. Compounds, urea compounds, silicon compounds, curryxarene and the like are preferred.
As the positive control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, an imidazole compound and the like are preferable. These charge control agents are used in an amount of 0.5 to 1 based on 100 parts by weight of the binder resin.
It is preferable to add 0 parts by weight.

For the purpose of imparting various properties, for example, the following additives are specifically used as toner additives.

As the lubricant, a fluororesin powder (such as fukavinylidene and polytetrafluoroethylene) and a fatty acid metal salt (such as zinc stearate and calcium stearate) are preferably used. As the charge control particles, metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like are preferably used.

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

The toner of the present invention can be obtained by, for example, a suspension polymerization method, a seed polymerization method, a dispersion polymerization method, or the like. When the suspension polymerization method is used, for example, a polymerizable monomer, a colorant, a polymerization initiator, and a styrene having a melting point of 35 to 8 are used.
A monomer composition comprising a wax at a temperature of 0 ° C., an aromatic oxycarboxylic acid and / or an azo dye, and other additives is prepared, contains a dispersant, and has a pH of 3 to 7. In an aqueous medium, the monomer composition is dispersed and granulated using, for example, a homogenizer or a homomixer. Thereafter, stirring is performed to such an extent that settling of the particles is prevented, and the polymerization reaction proceeds. The polymerization temperature is preferably 35
The polymerization is carried out at a temperature in the range of from 90 to 90 ° C, more preferably from 40 to 80 ° C. The temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers, by-products, etc., in the latter half of the reaction and / or after completion of the reaction, a part of the aqueous medium is distilled off. Is also good. After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried.

In the present invention, known dispersants can be used as dispersants. Specifically, for example, as inorganic oxides, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate ,
Examples thereof include calcium sulfate, barium sulfate, bentonite, silica, and alumina. As the organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like can be used. Preferably, as the poorly water-soluble inorganic dispersant, a poorly water-soluble inorganic dispersant among the above-mentioned inorganic oxides may be used. More preferably, it is preferable to use a poorly water-soluble inorganic dispersant which is an inorganic oxide as described above, is poorly water-soluble, and is soluble in an acid. These dispersants are added in an amount of 0.2 to 100 parts by weight of the polymerizable monomer.
It is preferred to use up to 2.0 parts by weight. Further, it is preferable to use 300 to 3000 parts by weight of water with respect to 100 parts by weight of the monomer composition to obtain an aqueous medium.

As these hardly water-soluble inorganic dispersants, commercially available inorganic dispersants may be used as they are. However, in order to obtain fine dispersant particles having a uniform particle size, the hardly water-soluble inorganic dispersant is stirred under high speed in a dispersion medium. An inorganic dispersant can also be formed. For example, in the case of tricalcium phosphate, under high-speed stirring,
A preferred dispersant can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride.

In the present invention, it is more preferable to adjust the pH to a desired range after preparing the aqueous medium containing the above-mentioned poorly water-soluble inorganic dispersant. By adjusting the pH, the hydrophilic compound containing a large amount of a polar group, such as an aromatic oxycarboxylic acid and / or an azo dye, is prevented from being eluted into an aqueous medium, and is effectively added internally to toner particles. This is because the expression is larger.

To make these dispersants finer, 0.001
A surfactant of up to 0.1% by weight may be used in combination. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate,
Sodium laurate, potassium stearate, calcium oleate and the like can be used. In the present invention, it is preferable not to use the above-mentioned surfactant.

Further, by producing the toner by the above-described production method, it is possible to suppress a decrease in the triboelectric charge amount under high temperature and high humidity and a decrease in the charging speed under low temperature and low humidity, and to suppress the contamination of the toner carrier. It has been found. The functional groups in the wax added internally in the toner and the aromatic oxycarboxylic acid and / or azo dye undergo hydrogen bonding, making it possible to complete the inclusion of these additives more completely.
Thus, it is considered that contamination of the toner carrier can be suppressed.

In the present invention, the preferable pH range is 3 to 7, but more preferably 4.
It is in the range of 5 to 6.0. When the pH exceeds 7.0,
The reaction of ionizing the aromatic oxycarboxylic acid and / or the azo dye and the wax itself and / or its derivative is easily promoted, and it is difficult to internally add the toner into the toner. In addition, in a low pH range such as a range where the pH is less than 3, other additives and a polymerizable monomer may be decomposed, which is not preferable.

In controlling the pH of the aqueous medium in the present invention, any method may be used. Specifically, for example, in addition to hydrochloric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid and the like, a commercially available pH adjuster may be used, and MgSO ₄ ,
CaCl ₂ , ZnSO ₄ , AlK (SO ₄ ) ₂ , Al ₂ (S
An acidic inorganic water-soluble salt such as O ₄ ) ₃ and ZnCl ₂ may be added. These may be used in combination of two or more as necessary. Preferably, it is at least one or more selected from hydrochloric acid, nitric acid, and sulfuric acid, and more preferably, hydrochloric acid.

In the present invention, the preparation of the monomer composition is preferably carried out at a temperature of 35 to 90 ° C., more preferably at a temperature of 35 to 80 ° C. Because the wax is in a so-called dissolved state, the wax contained in the monomer composition and the aromatic oxycarboxylic acid and / or the azo dye are mixed at a molecular level, whereby hydrogen bonding between the two is promoted, This is because the effect of improving inclusion in the toner particles and the effect of suppressing elution into the aqueous medium are increased.

In the present invention, as a polymerizable monomer used for producing a toner by a polymerization method, a vinyl polymerizable monomer capable of radical polymerization can be used.

Specifically, styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-ethylstyrene, p-tert-butylstyrene, etc .; acrylic acid, acrylic acid Methyl, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Acrylic acid esters of methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-methacrylic acid
-Butyl, isobutyl methacrylate, n-methacrylate
Methacrylates such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate, and benzyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxy Besides ethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc., alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl ether;
Diene compounds such as chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl ether, p-chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether, butadiene, acrylic acid, methacrylic acid, crotone Acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate, phosphoric acid-containing monomer, specifically, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, sulfonic acid group-containing monomer Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, acroylmorpholine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 4-
Vinylpyrrolidone, N-vinylpyrrolidone, 2-vinylimidazole, N-methyl-2-vinylimidazole,
N-vinylimidazole can be mentioned.

These monomers can be used alone or in combination of two or more.
A suitable polymer composition can be selected so as to obtain preferable characteristics.

According to the present invention, a high molecular weight component or a gel component can be contained. The introduction of such a component is achieved by using a crosslinking agent having two or more polymerizable double bonds per molecule. Specific examples of such a cross-linking agent include, for example, divinylbenzene, aromatic divinyl compounds such as divinylnaphthalene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, 1,3-
Butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6
-Hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate,
Examples thereof include compounds such as pentaerythritol tetramethacrylate, glycerol acroxydimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and two or more compounds may be appropriately mixed and used. Such a crosslinking agent can be previously mixed with the polymerizable mixture, or can be appropriately added during the polymerization as needed.

In the present invention, if necessary, any of those known as polymerization initiators can be used. Specific examples of such a polymerization initiator include, for example, 2,2′-azobis-
(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy 2, Azo or diazo polymerization initiators such as 4-dimethylvaleronitrile; 2,2′-azobis (2-aminodipropane) dihydrochloride;
Amidine compounds such as 2′-azobis (N, N′-dimethyleneisobutylamidine) and 2,2′-azobis (N, N′-dimethyleneisobutylamidine) dihydrochloride; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl per Oxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, peroxide-based polymerization initiators such as lauroyl peroxide and potassium persulfate, persulfide-based initiators such as ammonium persulfate, and the above-mentioned initiators Mixtures can be mentioned. The addition amount of the polymerization initiator is preferably in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer.

In the present invention, a known chain transfer agent, specifically, carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl dibromide ethylbenzene, ethane dibromide, Halogenated hydrocarbons such as ethane dichloride; hydrocarbons such as diazothioether, benzene, ethylbenzene and isopropylbenzene; mercaptans such as tertiary decyl mercaptan and n-dodecyl mercaptan; disulfides such as diisopropyl zantogen disulfide are added. You can also. These addition amounts are 0.001 to 10 parts by weight per 100 parts by weight of the polymerizable monomer.
A range of parts by weight is preferred.

The toner of the present invention can be used as a one-component developer or a two-component developer using a carrier.

When used as a two-component developer, for example, the magnetic carrier is composed of an element selected from iron, copper, zinc, nickel, cobalt, manganese and chromium alone or in a composite ferrite state. Examples of the shape of the magnetic carrier include a spherical shape, a fan shape, and an irregular shape. Further, the fine structure (for example, surface unevenness) of the surface state of the magnetic carrier can be controlled. Further, a coated carrier whose surface is coated with a resin can be suitably used. The average particle size of the carrier is preferably 10 to 100 μm, more preferably 20 to 100 μm.
５０50 μm. When preparing a two-component developer,
The toner concentration in the developer is preferably 2 to 15% by weight.

In the present invention, the measurement of the triboelectric charge amount and the charging speed of the toner is performed by the following method. Room temperature and normal humidity (23 ℃
/ 60% RH), high temperature and high humidity (30 ° C./90% RH), and low temperature and low humidity (15 ° C./10% RH), the toner and the carrier are left for 24 hours, and then blow-off method is performed in each environment. , The amount of triboelectric charge of the toner is measured.

FIG. 1 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount of toner. First, a mixture of a toner and a carrier having a weight ratio of 1:19 for measuring the triboelectric charge amount of 50 to 100 m
Samples are prepared by placing in a 1 volume polyethylene bottle and shaking by hand for 0.5-10 minutes. About 5 to 15 g of the above sample is placed in a metal measuring container 2 having a 500-mesh screen 3 at the bottom, and a metal lid 4 is placed. At this time, the weight of the entire measuring container 2 is weighed and W ₁ (g)
And Next, the suction device 1 (the portion in contact with the measurement container 2 is
In at least the insulator), the pressure of the vacuum gauge 5 is adjusted to 250 mmAq by adjusting the air volume control valve 6 by suctioning from the suction port 7. In this state, suction is performed for 2 minutes to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor whose capacity is C (μF).
And Weigh the entire measuring container after suction and weigh W ₂ (g)
And The triboelectric charge (mC / kg) of this toner is calculated by the following equation.

[0098]

(Equation 2)

When the charging speed is measured, the amount of frictional charge at each shaking time is measured, and the shaking time is plotted on the horizontal axis and the triboelectric charge is plotted on the vertical axis. Obtain from the slope.

[0100]

EXAMPLES (Example -1) 300 parts by weight of ion-exchanged water was charged with 0.1M-Na ₃ PO ₄ aqueous solution 250 parts by weight, followed by heating to 60 ° C., TK-homomixer (Tokushu Kika (Industrial product) at 12000 rpm.
To this, 35 parts by weight of a 1.0 M CaCl ₂ aqueous solution was gradually added to prepare an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Further, while measuring with a pH meter, hydrochloric acid was gradually added to adjust the pH to obtain an aqueous medium having a pH of 4.8.

As the aromatic oxycarboxylic acid, di-ter
Using 1 part by weight of t-butylsalicylic acid and 8 parts by weight of wax-1 having a melting point of 45 ° C. in styrene, a monomer composition was prepared under the following conditions. 80 parts by weight of styrene 20 parts by weight of n-butyl acrylate 8 parts by weight of copper phthalocyanine 2 parts by weight of negative charge control agent (iron complex of monoazo dye) 1 part by weight of di-tert-butylsalicylic acid 1 part by weight of wax-1 Department

The above material was heated to 55 ° C., and was uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer. The polymerization initiator 2,2′-azobis (2,4
-Dimethylvaleronitrile) was dissolved in 8 parts by weight to prepare a monomer composition.

The monomer composition was charged into the aqueous medium, and the monomer composition was dispersed in a nitrogen atmosphere at 55 ° C. while stirring with a TK homomixer at 12,000 rpm for 20 minutes, and granulated. did. Thereafter, the mixture was reacted for 12 hours while stirring with a paddle stirring blade. After the polymerization reaction, cool down,
Hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, drying, and classification to obtain toner particles.

To 100 parts by weight of the obtained toner particles, 2.0 parts by weight of silica fine particles-1 were externally added to obtain toner-1.

The number average particle size of the obtained toner-1 is 4.
The average circularity was 0.991. The particles having a circularity of less than 0.950 contained 8% by number, and the peak of the number frequency was 1.000. Further, the degree of aggregation of the toner was 6%.

A small amount of the above toner was placed on a sample table for SEM to which a carbon double-sided tape was attached, and platinum was deposited.
A SEM photograph of 000 times was taken. From the image obtained by enlarging the photograph by 400 times with a color copying machine (manufactured by CLC-800 Canon), the average length of the maximum length of one inorganic fine powder and the length in the vertical direction is determined by the particles of the inorganic fine powder. Diameter. The measurement was performed until the number of the measured inorganic fine powder reached 300, and the average value was determined. The average particle size of the inorganic fine powder was 85 nm.

Using 200 ml of tetrahydrofuran as a solvent, 10 g of the above toner was subjected to Soxhlet extraction for 12 hours, and the solvent was removed from soluble components in tetrahydrofuran using an evaporator. 100 ml of chloroform was added to the residue and stirred for 12 hours. The insolubles were collected by filtration, dissolved in deuterated tetrahydrofuran,
C ¹³ -NMR using EX400 manufactured by JEOL Ltd.
The measurement was carried out, the value was calculated from the integrated value of the peak, and the value of ([-CH _2- ] / [-OCO-]) contained in the wax was 20.

5 parts by weight of the above toner-1 and 95 parts by weight of a coated magnetic ferrite carrier (average particle size: 25 μm) coated with 1% by weight of a silicone resin were mixed.
A two-component developer was prepared.

The two-component type developer was subjected to room temperature and normal humidity (23 ° C. /
60% RH) and high temperature and high humidity (30 ° C./80% RH), and triboelectric charging under normal temperature and normal humidity (23 ° C./60% RH) and low temperature and low humidity (15 ° C./10% RH) The speed was compared.

Further, this two-component developer was introduced into a full-color digital machine (manufactured by CLC-800 Canon Inc.), and under a normal temperature and normal humidity environment, the contrast potential was set to 250 V, and the toner was successively replenished in the mono color mode. The degree of soiling of the sleeve and that of the cleaning blade when continuous copying of 5000 sheets were performed using an original having a ratio of 25% were compared.

Example 2 Same as Example 1 except that the pH of the aqueous medium was adjusted to 5.2 and 1 part by weight of azo dye-1 represented by the following chemical formula 1 was used as the azo dye. Thus, Toner-2 was prepared.

[0112]

Embedded image

The number average particle size of the obtained toner-2 is 4.
The average circularity was 0.989. The particles having a circularity of less than 0.950 contained 6% by number, and the peak of the number frequency was 0.997. Further, the degree of aggregation of the toner was 6%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Example 3 The pH of an aqueous medium was adjusted to 5.0, and di-tert- was used as an aromatic oxycarboxylic acid.
Toner-3 was prepared in the same manner as in Example 1, except that 0.4 parts by weight of butylsalicylic acid and 0.4 part by weight of azo dye-1 represented by the above-mentioned formula 1 were used as the azo dye.

The number average particle size of the obtained toner-3 is 4.
The average circularity was 0.986. The particles having a circularity of less than 0.950 contained 8% by number, and the peak of the number frequency was 0.993. Further, the aggregation degree of the toner was 8%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Example 4 The pH of an aqueous medium was adjusted to 4.8, and 5-tert-
0.5 parts by weight of octylsalicylic acid, 4 parts by weight of wax-2 having a melting point of 55 ° C. in styrene, and 2.0 parts by weight of silica fine particles-2 per 100 parts by weight of toner particles Except for adding, toner 4 was produced in the same manner as in Example 1.

The number average particle size of the obtained toner-4 is 3.
The average circularity was 0.984. The particles having a circularity of less than 0.950 contained 12% by number, and the peak of the number frequency was 0.991.
The aggregation degree of the toner was 13%. The value of ([-CH _2- ] / [-OCO-]) contained in the wax was determined to be 24. The average particle size of the silica fine particles-2 was 176 nm.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Example-5) The pH of an aqueous medium was adjusted to 4.8, and 0.5 parts by weight of azo dye-2 represented by the following chemical formula-2 and 4 parts by weight of wax-2 were used as azo dyes. Toner 5 was produced in the same manner as in Example 1, except that 2.0 parts by weight of silica fine particles-2 was externally added to 100 parts by weight of toner particles.

[0122]

Embedded image

The number average particle size of the obtained toner-5 is 3.
The average circularity was 0.985. The particles having a circularity of less than 0.950 contained 11% by number, and the peak of the number frequency was 0.993.
The degree of aggregation of the toner was 12%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Example 6 The pH of an aqueous medium was adjusted to 5.8, and 5-tert-octylsalicylic acid was added to 0.08.
Toner-6 in the same manner as in Example 1, except that 4 parts by weight of wax-1 and 4 parts by weight of wax-1 and 2.0 parts by weight of silica fine particles-2 were added to 100 parts by weight of toner particles.
Was prepared.

The number average particle size of the obtained toner-6 is 3.
The average circularity was 0.979. The particles having a circularity of less than 0.950 contained 14% by number, and the peak of the number frequency was 0.984.
The aggregation degree of the toner was 18%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Example 7 The pH of an aqueous medium was adjusted to 5.8, and 2.4 parts by weight of azo dye-2 represented by the above-mentioned chemical formula-2 and 8 parts by weight of wax-1 were used as azo dyes. A toner 7 was produced in the same manner as in Example 1, except that the toner was used and 2.0 parts by weight of silica fine particles-3 was externally added to 100 parts by weight of the toner particles.

The number average particle size of the obtained toner-7 is 4.
The average circularity was 0.974. The particles having a circularity of less than 0.950 contained 19% by number, and the peak of the number frequency was 0.980.
The aggregation degree of the toner was 16%. The average particle size of the silica fine particles-3 was 27 nm.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Example 8 The pH of an aqueous medium was adjusted to 6.4, and 2.0 parts by weight of azo dye-1 represented by the above-mentioned formula 1 and 12 parts by weight of wax-2 were used as azo dyes. Except for using it, Toner-8 was produced in the same manner as in Example-1.

The number average particle size of the obtained toner-8 is 6.
The average circularity was 0.971. The particles having a circularity of less than 0.950 contained 24% by number, and the peak of the number frequency was 0.986.
Further, the aggregation degree of the toner was 23%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 1) The pH of an aqueous medium was adjusted to 7.2, and 0.008 parts by weight of azo dye-1 represented by the above formula 1 and 8 parts by weight of wax-1 were used as azo dyes. Except for using toner 9 in the same manner as in Example 1,
Was prepared.

The number average particle size of the obtained toner-9 is 4.
The average circularity was 0.948. The particles having a circularity of less than 0.950 contained 32% by number, and the peak of the number frequency was 0.976.
Further, the aggregation degree of the toner was 31%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 2) The pH of the aqueous medium was adjusted to 8.1, and 0.002 parts by weight of the azo dye-2 represented by the aforementioned chemical formula-2 and 15 parts by weight of the wax-2 as the azo dye. Except for using, the toner was prepared in the same manner as in Example 1.
10 was produced.

The number average particle diameter of the obtained toner-10 was 6.8 μm, and the average circularity was 0.945.
The particles having a circularity of less than 0.950 are 36
% Number, and the peak of the number frequency was 0.961. Further, the aggregation degree of the toner was 34%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 3) The pH of the aqueous medium was adjusted to 8.1, and 5-tert-
5 parts by weight of octyl salicylic acid, 8 parts by weight of wax-3 having a melting point of 82 ° C. in styrene, and 2 parts of silica fine particles-3 per 100 parts by weight of toner particles.
A toner 11 was produced in the same manner as in Example 1, except that 0 part by weight of the toner was externally added.

The number average particle size of the obtained toner-11 was 5.4 μm, and the average circularity was 0.946.
Particles having a circularity less than 0.950 are 34
It contained a number%, and the peak of the number frequency was 0.962. The aggregation degree of the toner was 48%. Further, the value of ([-CH _2- ] / [-OCO-]) contained in the wax was found to be 53.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 4) The pH of an aqueous medium was adjusted to 9.4, 8 parts by weight of azo dye-1 represented by the above formula 1 as an azo dye, and the melting point in styrene was 33 ° C.
Was prepared in the same manner as in Example 1, except that 30 parts by weight of Wax-4 was used.

The number average particle size of the obtained toner-12 is 1
The average circularity was 1.6 μm and the average circularity was 0.912.
The particles having a circularity of less than 0.950 are 43
The number% was contained, and the peak of the number frequency was 0.938. Further, the aggregation degree of the toner was 38%. Also,
([-CH _2- ] / [-OCO
-]) Was determined to be 4.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 5) The pH of the aqueous medium was adjusted to 4.9, 4 parts by weight of wax-3 was used, and 2.0 parts by weight of silica fine particles-3 were added to 100 parts by weight of toner particles. Except for external addition, the same procedure as in Example 1 was repeated for toner 1
3 was produced. However, sphering treatment by heating was performed during drying.

The number average particle diameter of the obtained toner-13 was 5.3 μm, and the average circularity was 0.997.
The particles having a circularity of less than 0.950 contained 7% by number, and the peak of the number frequency was 1.000.
Further, the aggregation degree of the toner was 49%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example-6) The pH of the aqueous medium was adjusted to 5.3, 20 parts by weight of wax-4 was used, and 2.0 parts by weight of silica fine particles-1 was added to 100 parts by weight of toner particles. A toner was prepared in the same manner as in Example 1 except that the toner was externally added.
14 was produced. However, sphering treatment by heating was performed during drying.

The number average particle diameter of the obtained toner-14 was 8.4 μm, and the average circularity was 0.996.
Particles having a circularity of less than 0.950 are 12
It contained a number%, and the number frequency peak was 1.000. Further, the aggregation degree of the toner was 44%.

A two-component developer was prepared in the same manner as in Example 1, and the same evaluation was performed.

Table 1 shows the used waxes, Table 2 shows the inorganic fine powder, and Table 3 shows the properties of the toner. Table 4 shows the evaluation results of the examples and comparative examples.

[0153]

[Table 1]

[0154]

[Table 2]

[0155]

[Table 3]

[0156]

[Table 4]

[0157]

According to the present invention, it is possible to provide a small particle size toner which is excellent in environmental stability and does not contaminate a toner carrier or the like.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of a toner.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Hashimoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Satoshi Handa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Keiji Kawamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA06 AA15 AA21 AB06 CA14 CA21 CA25 DA01 DA07 EA03 EA05 EA07 EA10

Claims (9)

[Claims] 1. At least (i) a binder resin, (ii) a colorant, (iii) a wax and (iv) an aromatic oxycarboxylic acid represented by the following general formula (1) and represented by the following general formula (2) A dry toner containing at least one compound selected from the group consisting of azo dyes, wherein the total amount of the compounds is 0.01 to 0.01% by weight of the toner.
A wax having a melting point of 35 to 80 ° C. in a styrene monomer in an amount of from 0.5 to 10% by weight based on the weight of the binder resin; The average circularity is 0.950 to 0.995 in the degree distribution, and 1 to 30% by number of particles having a circularity in the range of less than 0.950 are contained. 950 or more dry toner. Embedded image Embedded image [Wherein, Ar represents an aryl group, which may have a substituent, and X and Y represent -O-, -CO-, -NH
-Or -NR- (R represents an alkyl group having 1 to 4 carbon atoms), and D and F represent -H, -OH, -Na or-.
K is shown. ] 2. The toner has an average particle diameter of 10 to 50.
An inorganic fine powder in a range of 0 nm is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the toner, and the degree of aggregation of the toner is in a range of 1 to 30%. Item 1. The dry toner according to Item 1. 3. An abundance ratio ([—CH ₂ —] / [— OCO—]) of an ethylene unit (—CH ₂ —) and an ester bond (—OCO—) contained in the wax is from 5 to 5.
3. The dry toner according to claim 1, further comprising a polar wax in a range of 0. 4. The toner has a number average particle diameter of 2 to 8 μm.
4. The dry toner according to claim 1, wherein m is in the range of m. (I) at least a polymerizable monomer, a colorant, a polymerization initiator, and a melting point in styrene of 35 to 80.
° C, and an aromatic oxycarboxylic acid represented by the following general formula (1) and / or an azo dye represented by the following general formula (2) are mixed in a temperature range of 35 to 90 ° C to form a simple mixture. Preparing a monomer composition, and (II) p
Granulating the monomer composition in an aqueous medium in which H is in the range of 3 to 7, and (III) mixing the polymerizable monomer granulated in the aqueous medium at 35 to 95 ° C. Polymerizing in a temperature range. Embedded image Embedded image [Wherein, Ar represents an aryl group, which may have a substituent, and X and Y represent -O-, -CO-, -NH
-Or -NR- (R represents an alkyl group having 1 to 4 carbon atoms), and D and F represent -H, -OH, -Na or-.
K is shown. ] 6. The method according to claim 5, wherein the aqueous medium is an aqueous medium containing a poorly water-soluble inorganic dispersant. 7. The method for producing a dry toner according to claim 5, wherein the pH is in the range of 4 to 6. 8. The method according to claim 5, wherein the content of the aromatic oxycarboxylic acid and / or the azo dye in the monomer composition is in the range of 0.01 to 3% by weight. Or a method for producing a dry toner. 9. The method for producing a dry toner according to claim 5, wherein the content of the wax in the monomer composition is in a range of 0.5 to 10% by weight. .