JP2003043748A - Toner and method for forming full color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent transparency of a yellow projected image by an OHP and little fog on a transfer material at high temperature and high humidity. SOLUTION: The toner contains a compound of a hydroxycarboxylic acid expressed by formula (I) and a bivalent or trivalent metal. The coloring agent is a single material of C.I.Pigment Yellow 180 or in combination with C.I.Solvent Yellow 162. The tetrahydrofuran-soluble component of the toner shows 10,000 to 600,000 weight average molecular weight by the gel permeation chromatography and the average circularity of the toner ranges from 0.920 to 0.995 with <0.040 standard deviation of the circularity measured by a flow type particle image measuring device.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet method, and a full color image forming method.

[0002]

2. Description of the Related Art Conventionally, digital full-color copying machines and printers have been put into practical use, and high-quality images having excellent color reproducibility without color unevenness as well as resolution and gradation have been obtained.

In a digital full-color copying machine, a color image original is color-separated by B (blue), G (green), and R (red) color filters, and then has a dot diameter of 20 to 70 μm corresponding to the original image. Latent image Y
(Yellow), M (Magenta), C (Cyan), BK
It develops by utilizing the subtractive color mixing action using each color developer of (black), but it is necessary to transfer a large amount of the developer from the photoconductor to the transfer material as compared with the black-and-white copying machine, and further high image quality in the future. In order to respond to the demand for finer dots, it is expected that the developer will be required to have a finer grain size for finer dots.

However, if the toner particle size is made smaller in accordance with the demand for higher image quality, the resolution and sharpness of a full-color image will certainly be satisfactory, but it has been found that there are various effects associated with finer particles. Came.

The problem is that the smaller the toner particle size, the more unevenly distributed the colorant is, and the more easily the charging characteristics are affected.

Further, in recent years, the copying apparatus has begun to be used not only as a general copying machine for copying an original document but also as a printer as an output of a computer or a personal copy for individuals.

In addition to the fields typified by such laser beam printers, the development of plain paper faxes to which the basic engine is applied is rapidly developing.

In particular, there is a demand for smaller size, lighter weight, higher speed, higher image quality, higher reliability, and especially higher speed in color printers and personal color copies for personal computers, where rapid market growth is expected. It is an essential issue how to maintain strength and high reliability in high-speed printing. When continuous paper feeding is performed at high speed, the temperature rise in the machine tends to be severe, and improvement of toner characteristics against it is also an important issue.

Therefore, a toner having a good charging property by improving the dispersion of each color of the color toner more than before,
Toner that is less likely to deteriorate due to temperature rise during continuous paper feeding is required.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and a full-color image forming method which can solve the above-mentioned problems.

An object of the present invention is to provide a toner excellent in transparency of a yellow projected image of an OHP (overhead projector) and an image forming method.

A further object of the present invention is to provide a toner and an image forming method which cause less fogging on a transfer material at high temperature and high humidity and less toner scattering.

A further object of the present invention is to provide a toner and an image forming method which have good transferability at high temperature and high humidity.

A further object of the present invention is to provide a toner excellent in red and blue fixing properties at high temperature and high humidity, and an image forming method.

A further object of the present invention is to provide a toner and an image forming method which have a wide color space of a full color projected image of an OHP (overhead projector) and are excellent in transparency.

[0016]

The present invention contains at least a binder resin, a colorant, a release agent, and a compound of a hydroxycarboxylic acid represented by the following formula (I) and a divalent or trivalent metal. The toner is a C.I. I. Pig
ment Yellow 180 alone or C.I.
I. Pigment Yellow 180 and C.I.
I. Solvent Yellow 162, which is a combination of gel permeation chromatography (G) of a soluble component of tetrahydrofuran (THF) in the toner.
(PC) weight average molecular weight of 10,000 to 600
000 and the average circularity of the toner measured by the flow type particle image measuring device is 0.920 to 0.995.
And a toner having a circularity standard deviation of less than 0.040.

[0017]

[Chemical 3] (In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a nitro group,
It represents a substituent selected from the group consisting of a cyano group, an amino group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. )

The present invention uses a toner containing at least a binder resin, a colorant, a release agent, and a compound of the hydroxycarboxylic acid represented by the above formula (I) and a divalent or trivalent metal. In the full-color image forming method, the yellow colorant in the toner is C.I. I. Pigment
Yellow 180 alone or C.I. I. Pigm
ent Yellow 180 and C.I. I. Solve
nt Yellow 162 in combination, the soluble component of tetrahydrofuran (THF) in the toner has a weight average molecular weight of 10,000 to 600,000 in gel permeation chromatography (GPC), and is measured by a flow type particle image measuring device. The toner has an average circularity of 0.920 to 0.995 and a standard deviation of circularity of less than 0.040.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A toner containing a hydroxycarboxylic acid derivative has been filed for the purpose of improving a stable charge amount over a long period of time and the transparency of an OHP sheet (Japanese Patent Laid-Open No. 07-084409, Japanese Patent Laid-Open No. 07-84409). 08-26
2800). However, C.I. I. Pigment
Yellow 12.14, C.I. I. Solvent
Yellow 21.77.114, C.I. I. Disp
In the case of using the yellow colorant such as erse Yellow 164, the above-mentioned items are not always satisfactory. Further, in the formation of a full-color image, the vividness of the projected image is still not sufficient.

On the other hand, as a result of intensive investigations by the present inventors, a compound of a hydroxycarboxylic acid represented by the following formula (I) and a divalent or trivalent metal and a yellow colorant in the above combination were obtained. By doing so, it was found that the transparency is improved as compared with the conventionally known example.

Further, a yellow colorant in the above combination,
Of a toner containing a magenta colorant and a cyan colorant,
It has been found that the above problems can be improved by setting the circle-equivalent number average diameter, the average circularity, and the circularity standard deviation within a certain range.

[0022]

[Chemical 4] (In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a nitro group,
It represents a substituent selected from the group consisting of a cyano group, an amino group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. )

By the combination as described above, it is possible to maintain the same charging ability as in the case of using the compound of the aromatic oxycarboxylic acid and the metal, and in addition, since the standard deviation of the circularity is small, it is developed and transferred. It has become possible to manufacture a toner that is resistant to environmental changes due to the small difference in the charge amount distribution between the toners. As a result, fog on the paper during continuous paper feeding at high temperature and high humidity was reduced, and toner scattering was improved as compared with the known art.

Further, by combining the above hydroxycarboxylic acid derivative and the colorant, the binder resin has weak crosslinkability as compared with the conventional charge control agent for color toner. In addition to this, the weight average molecular weight, the circularity and the standard deviation of the circularity of the soluble component of tetrohydrofuran (THF) are added, so that the continuous paper feeding, especially the continuous paper feeding under high temperature and high humidity is performed. The generation of toner agglomerates, which are likely to occur in the developer packing section in the developing machine, could be reduced. Further, it is possible to reduce the embedding of the external additive on the toner surface. From this, it is possible to significantly improve the transfer failure due to the aggregates in the continuous paper feeding under high temperature and high humidity.

The hydroxycarboxylic acid (unsubstituted or substituted benzylic acid) which is a compound of the hydroxycarboxylic acid and the divalent or trivalent metal of the present invention has the following structure.

[0026]

[Chemical 5] (In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a nitro group,
It represents a substituent selected from the group consisting of a cyano group, an amino group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. )

The divalent or trivalent metal is not particularly limited, but is preferably B, Zn, Ni, Co or M.
n and Al are good. More preferably, Zn, Al, etc. have high charging ability and are good.

The counter ion is not particularly limited and any counter ion can be used. For example, hydrogen, lithium, sodium, potassium, ammonium, alkylammonium, and the like.

The metal compound is used in an amount of 0.01 to 10 parts by mass, more preferably 0.05, based on 100 parts by mass of the binder resin.
It is preferable to use 5 to 5 parts by mass. The binder resin referred to here may be any ordinary resin, and more preferably a vinyl resin.

If the addition amount is less than 0.01 parts by mass,
Insufficient charging performance and poor fogging of the initial image on paper.
When the amount is more than 10 parts by mass, the dispersion of the metal compound itself is poor, and accordingly, the dispersion of the colorant in the toner is also poor, resulting in a toner having non-uniform charging.

When the toner of the present invention is a polymerized toner, the metal compound may be contained in either the water phase or the oil phase.

The colorant C.I. I. Solvent Yel
low 162 / C. I. Pigment Yellow
The ratio of w 180 is preferably 0 to 3.0, more preferably 0 to 2.0. If the ratio exceeds 3.0, the light resistance is not always sufficient.

The magenta colorant used in the image forming method of the present invention is preferably a quinacridone type and / or an azo type, and more preferably a quinacridone type solid solution pigment. The solid solution pigment is generally obtained by dehydration and pigmentation when two or more kinds of magenta pigments are mixed in the dehydration step of the pigment production process and the step before the pigmentation step.

As a combination of solid solutions, those having a structure as close as possible are used in combination due to the stability of the structure and the ease of production. In particular, the substituted quinacridone pigment and the unsubstituted quinacridone pigment shown below are used in combination from the viewpoint of excellent light resistance and coloring power. Magenta solid solution pigment (1): C.I. I. Pigment
Red 122 and C.I. I. Pigment Violet
solid solution with magenta solid solution pigment (2): C.I. I. Pigment
Red 202 and C.I. I. Pigment Viol
solid solution with et 19

C. I. Pigment Violet
Although the light resistance and the coloring power of 19 are likely to change depending on its crystal structure, they are stabilized by forming a solid solution. Furthermore, the hue of the solid solution is C.I. I. Pigment Viol
By changing the compounding ratio of et 19 and the condition setting at the time of crystallization, it is possible to widen the hue space of the solid solution without impairing the saturation and brightness of the pigment. In order to make the saturation and coloring power of the solid solution pigment more preferable values, the compounding ratio of the substituted quinacridone pigment and the unsubstituted quinacridone pigment in the solid solution pigment is preferably 85:15 to 30:70, more preferably Is preferably 80:20 to 50:50.

The cyan colorant used in the image forming method of the present invention is preferably a phthalocyanine type, more preferably a copper phthalocyanine type C.I. I. Pigme
ntBlue 15 is desired.

When the metal compound is combined with the magenta colorant and the cyan colorant, the fixability is significantly improved when the amount of toner applied is high at high temperature and high humidity. Although the reason has not been clarified at present, it is considered that the reason is that the sublimability of the metal compound due to the heat of fixing is small.

The colorant is preferably contained in an amount of 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the image density will not be sufficient and the image will be poor. 1
When it exceeds 5 parts by mass, the dispersion in the toner becomes insufficient and the charging becomes non-uniform. Further, in the case of the polymerized toner, the granulating property is adversely affected, and a uniform particle size distribution cannot be obtained. The colorant may or may not be surface-treated.

The preferred physical properties of the toner of the present invention are described below.

In the number-based circle-equivalent diameter-circularity scattergram of the toner measured by a flow-type particle image measuring device, the average circle-equivalent number diameter D ₁ (μm) of the toner is 2
To 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.0.
It is preferably less than 40. More preferably, the average circularity is 0.
965 to 0.990 with a circularity standard deviation of 0.035
It is better to be less than.

In the number-of-toner-based circle equivalent diameter-circularity scattergram measured by the above-mentioned flow type particle image measuring device, the toner particles having a circularity of less than 0.950 are 15% by number or less. preferable.

By reducing the particle diameter of the toner circle-equivalent number average diameter D ₁ (μm) to 2 to 10 μm, the reproducibility of the outline portion of an image, especially a character image or a line pattern, is improved. Become. However, generally, when the toner particles are reduced in size, the abundance ratio of toner of fine particles is inevitably increased, which makes it difficult to uniformly charge the toner and causes image fogging, and also the surface of the electrostatic latent image bearing member. Also, the adhesive force to the toner carrier is increased, and as a result, the developing characteristics are deteriorated.

However, when the toner of the present invention has a circularity standard deviation of less than 0.040, preferably less than 0.035, the problem relating to developability can be greatly improved.

The reason therefor is a toner containing the compound of hydroxycarboxylic acid according to the present invention and a divalent or trivalent metal, and by combining with the colorant, the toner particles are favorably charged. Since the characteristics can be uniformly given to each toner and good triboelectric charge imparting and toner carrying force can be given from the toner layer regulating member and the toner carrier, the toner charge amount and the toner coat amount on the toner carrier are appropriate. I think it is because it becomes possible to do something like this.

The average circularity of the circularity frequency distribution of the toner particles is 0.920 to 0.995, preferably 0.9.
By setting it to 50 to 0.995, and more preferably 0.965 to 0.990, the transferability of the toner exhibiting a small particle size, which was difficult in the past, is significantly improved and the developing ability for a low potential latent image is improved. Also significantly improves. In particular, the above tendency is very effective when developing a minute spot latent image of a digital system or when forming a full-color image in which a large number of transfers are performed by using an intermediate transfer member, and the matching with an image forming apparatus is also good. It will be

The circle-equivalent number average diameter, circularity and their frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the shape of toner particles. In the present invention, flow type particles are used. Image measuring device FPIA-10
The measurement was performed using a 00 type (manufactured by Toa Medical Electronics Co., Ltd.) and calculated using the following formula.

[0047]

[Equation 1]

Here, the "particle projection area" is the area of the binarized toner particle image, and the "perimeter of the particle projection image".
Is defined as the length of the contour line obtained by connecting the edge points of the toner particle image.

The circularity in the present invention is an index showing the degree of unevenness of the toner particles, and it is 1.00 when the toner particles are completely spherical, and the smaller the surface shape becomes, the smaller the circularity is. Become.

In the present invention, the circle-equivalent number average diameter and the particle size standard deviation SDd, which mean the average value of the particle size frequency distribution based on the number of toner particles, are the particle size (center value) at the dividing point i of the particle size distribution. It is calculated from the following equation, where di is the frequency and fi is the frequency.

[0051]

[Equation 2]

Further, the average circularity and the circularity standard deviation SDc, which mean the average value of the circularity frequency distribution, are given by the following formula, where the circularity (center value) at the dividing point i of the particle size distribution is ci and the frequency is fci. Calculated from the formula.

[0053]

[Equation 3]

As a specific measuring method, 10 ml of ion-exchanged water from which impure solids and the like have been removed beforehand is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant into the container. Then, 0.02 g of a measurement sample is further added and uniformly dispersed. As a means for dispersing, an ultrasonic disperser UH-50 type (manufactured by SMT) equipped with a titanium alloy chip of 5φ as a vibrator was used, and a dispersion treatment for 1 to 5 minutes was performed to obtain a dispersion liquid for measurement. To do. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.

To measure the shape of toner particles, the flow type particle image measuring device is used, and the toner particle concentration at the time of measurement is 30.
The concentration of the dispersion liquid is readjusted so as to be 0.00 to 10,000 particles / μl, and 1000 or more toner particles are measured. After the measurement, using this data, the average number of circle-equivalent number diameters of toner, the circularity frequency distribution, and the like are obtained.

Tetrahydrofuran (THF) of the toner
Of the soluble component of GPC in gel permeation chromatography (GPC) has a weight average molecular weight of 10,000 to 6
00000, preferably a weight average molecular weight of 500
It is preferable that the weight average molecular weight is from 00 to 400,000, more preferably from 70,000 to 400,000.

When the weight average molecular weight was less than 10,000, the toner was largely deteriorated due to durability and the transferability was remarkably deteriorated. Further, when fixing is performed with an oilless fixing device, there occurs a problem that the image surface of the OHT sheet is roughened and the projected image of yellow toner is dull.

When the weight average molecular weight exceeds 600,000, the toner cannot be sufficiently melted at the fixing temperature, and the yellow projected image becomes dull. Further, during the production by the polymerization method, the dispersion of the charge control agent and the colorant in the toner is deteriorated in the step of producing a high molecular weight component, and as a result, there are problems such as fog and toner scattering in the machine. Further, the low temperature fixability also tends to be deteriorated.

A method for measuring the molecular weight distribution of the THF-soluble component of the toner will be described.

A sample for GPC measurement is prepared as follows. The toner is put in tetrahydrofuran (THF), left for several hours, shaken well, mixed well with THF, and left to stand for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. Then sample processing filter (pore size 0.45-0.5μ
m, for example, Mysholydisc H-25-5 manufactured by Tosoh Corp., Excicrodisc 25CR Gelman Science Japan Ltd., etc.) can be used as a GPC sample.

The toner concentration is such that the resin component is 0.5 to 5 mg.
Adjust so that it becomes / ml.

The molecular weight and molecular weight distribution by GPC of the THF-soluble component of the toner are measured by the following method. 40 ° C
The column is stabilized in the heat chamber of the above, and THF as a solvent is caused to flow at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected into the column at this temperature for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polyester sample for creating a calibration curve,
For example, it is suitable to use a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK and at least about 10 points. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, Shodex manufactured by Showa Denko KK
GPC KF-801, 802, 803, 804, 80
5,806,807,808P combination TSKgel G1000H (H _XL ), G2000 manufactured by Tosoh Corporation
H (H _XL ), G3000H (H _XL ), G4000H (H
_XL ), G5000H (H _XL ), G6000H (H _XL ),
A combination of G7000H (H _XL ) TSKguardcolumn is mentioned. In particular, the column configuration is A-801, 802, 803, 804, 805 manufactured by Showa Denko KK,
A combination of 806 and 807 is preferable.

The THF insoluble component of the toner is 0 to 50%.
Is preferable, and more preferably 3 to 30%.

The measurement of the THF insoluble matter will be described.

The THF-insoluble matter refers to a mass ratio of a substance insoluble in the THF solvent in the toner. The THF-insoluble matter is defined as a value measured as follows.

About 1.0 g of the toner sample is weighed (W1
g), put it in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), apply it to a Soxhlet extractor, and use THF10 as a solvent.
After extracting with 0 to 200 ml for 6 hours and evaporating the soluble component extracted with a THF solvent, 100
After vacuum drying at 0 ° C. for several hours, the amount of the THF-soluble resin component is weighed (W2g). The THF insoluble content in the toner is calculated from the following formula.

[0067]

[Equation 4]

The amount of the release agent of the toner is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, per 100 parts by mass of the binder resin.

When the amount of the releasing agent is less than 1 part by mass, the fixing property on the high temperature side is deteriorated, and the sheet is wound around the fixing roller when fixing the OHP sheet. When the amount of the release agent exceeds 40 parts by mass, the fluidity of the toner deteriorates, and the developability and transferability deteriorate sharply.

The MELT INDEX value (MI value; g / 10 min) of the toner of the present invention is preferably 0.1 to 100. It is more preferably 1 to 80.

When the MI value is less than 0.1, the toner is not sufficiently melted even at the fixing temperature, and the transparency of the yellow projected image is poor and dull. When the MI value exceeds 100, toner agglomerates are likely to be generated in the developer packing portion in the developing machine, and the external additive is largely embedded in the toner surface, which deteriorates the transferability in durability.

The method for measuring the MI value of the toner of the present invention is described in J
It is performed according to the A method of IS standard K7210. Then, the measured value is converted into a 10-minute value.

The toner of the present invention has an aggregation degree of 1 to 30%,
It is more preferably 4 to 20% from the viewpoint of developability. When the toner cohesion is small, the fluidity of the toner is high, and when the cohesion is large, the fluidity of the toner is low.

The aggregation degree of the toner is measured by the following method.

Using a vibrating screener of a powder tester (manufactured by Hosokawa Micron Co.), 400 mesh, 20
4 meshes of 0 mesh and 100 mesh so that they overlap with each other in ascending order of mesh openings, that is, 100 mesh is the highest rank.
The sieves of 00 mesh, 200 mesh, and 100 mesh are piled up in this order and set. This set 100 mesh
The sample was added on the sieve of No. 1, the input voltage to the shaking table was set to 15 V, the amplitude of the shaking table at that time was adjusted to be in the range of 60 to 90 μm, and vibration was applied for about 25 seconds, and then,
The mass of the sample remaining on each sieve is measured, and the aggregation degree is obtained based on the following formula. The smaller the value of the degree of aggregation, the higher the fluidity of the toner.

[0076]

[Equation 5]

The method for producing the toner of the present invention is not particularly limited, but is disclosed in Japanese Patent Publication No. 36-10231, Japanese Patent Publication No. 59-53856, and Japanese Patent Publication No. 59-6.
A method of directly producing a toner by using a suspension polymerization method described in Japanese Patent No. 1842; a soap-free method of producing a toner particle by being directly soluble in a monomer and being directly polymerized in the presence of a water-soluble polymerization initiator. Production of toner particles by an emulsion polymerization method typified by a polymerization method can be mentioned. Further, production of interfacial polymerization method such as microcapsule manufacturing method, in situ polymerization method, coacervation method and the like can also be mentioned. Furthermore, JP-A-62-106473 and JP-A-63-18625.
An interface association method, for example, as disclosed in Japanese Patent Publication No. 3, which obtains particles having a desired particle size by aggregating at least one kind of fine particles is also included.

A suspension polymerization method is particularly preferable because toner particles having a small particle diameter can be easily obtained. Further, a seed polymerization method in which a monomer is further adsorbed on the obtained polymer particles and then the resultant is polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to disperse or dissolve the polar compound in the adsorbed monomer. When suspension polymerization is used as the method for producing toner particles, the toner particles can be produced directly by the following production method. A monomer composition in which a low softening point substance such as wax, a colorant, a polymerization initiator, a cross-linking agent, and other additives are added to a monomer and uniformly dissolved or dispersed by a homogenizer or an ultrasonic disperser. Are dispersed in an aqueous medium containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer, or the like. Preferably, the stirring speed and time are adjusted so that the droplets of the monomer composition have a desired toner particle size,
Granulate. After that, stirring may be performed to the extent that the particle state is maintained and the particles are prevented from settling due to the action of the dispersion stabilizer. Polymerization temperature is 40 ° C or higher, usually 50 to 90
Polymerization is carried out at a temperature of ℃ (preferably 55 to 85 ℃). The temperature may be raised in the latter half of the polymerization reaction, and if necessary, pH
You can change it. Further, in order to remove unreacted polymerizable monomers, by-products, etc. which cause odor during fixing of the toner, the aqueous medium may be partially distilled off in the latter half of the reaction or after the reaction. After the reaction is completed, the produced toner particles are collected by washing and filtration and dried.

The pH in the aqueous medium during granulation is not particularly limited, but it is preferably pH 4.5 to 8.5, more preferably pH 4.5 to 6.0.

The materials of the polymerization toner will be described below.

As the polymerizable monomer used in the toner of the present invention, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p- n-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy Styrene, styrene derivatives such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso
-Butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl Acrylic polymerizable monomers such as acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert
-Butyl methacrylate, n-amyl methacrylate,
Methacrylic polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl acetate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone. Can be mentioned.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,
2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

In the present invention, the above monofunctional polymerizable monomers may be used alone or in combination of two or more kinds, or
The monofunctional polymerizable monomer and the polyfunctional polymerizable monomer described above are used in combination. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

An oil-soluble initiator is preferably used as the polymerization initiator used in the polymerization of the above-mentioned polymerizable monomer. For example, as the oil-soluble initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,
Azo compounds such as 4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) and 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, Diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate Rate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxy Id such as peroxide type initiators.

As the water-soluble initiator, ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-
Dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, 2,2′-azobisisobutyronitrile sodium sulfonate, sulfuric acid Examples include ferrous iron or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, it is possible to further add and use a chain transfer agent, a polymerization inhibitor or the like.

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,
And divinyl compounds such as divinyl sulfide and divinyl sulfone; and compounds having 3 or more vinyl groups. These are used alone or as a mixture.

The dispersion stabilizer used in the present invention includes
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ，
Examples thereof include hydroxyapatite. Usually, it is preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition.

As the organic compound, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like are used. It is preferable to use 0.2 to 2.0 parts by mass of these dispersants with respect to 100 parts by mass of the polymerizable monomer.

Dispersion stabilizers preferably used in the present invention include sparingly water-soluble metal salts of sulfuric acid, carbonic acid, phosphoric acid, pyrophosphoric acid and polyphosphoric acid, which are mixed with acid alkali metal salts under high speed stirring in a dispersion medium. It is preferably prepared by reaction with a metal halide salt.

To make these dispersants finer, 0.001 to
You may use 0.1 mass% of surfactant together. 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 are preferably used.

In the present invention, a condensation compound may be added.

The condensed compound has a weight average molecular weight (Mw).
Is 6,000 to 100,000, preferably 6,50
0 to 85,000 is good. Further 6,500 to 4
5,000 is better. When the weight average molecular weight is less than 6,000, the external additive on the surface of the toner particles is likely to be buried due to the durability in continuous paper feeding, and the transferability is likely to be deteriorated, as compared with those in the optimum range. When the weight average molecular weight exceeds 100,000, it takes a lot of time to dissolve the condensation compound in the polymerizable monomer.
Furthermore, the viscosity of the polymerizable monomer composition increases, and it becomes difficult to obtain toner particles having a small particle size and a uniform particle size distribution.

The condensed compound has a number average molecular weight (Mn).
Is 3,000 to 80,000, preferably 3,50
0 to 60,000 is good. More preferably 3,500
Or 12,000 is good. The condensed compound has a main peak value (Mp) of the molecular weight distribution in gel permeation chromatogram (GPC) of 4,500 to 40,000, preferably 6,000 to 30,000.
0 is good. More preferably 6,000 to 20,000
Is good. Outside the above range, the same tendency as in the case of the weight average molecular weight is exhibited.

The condensed compound has an Mw / Mn of 1.2 to 3.0, more preferably 1.5 to 2.5. Mw
If / Mn is less than 1.2, the durability and offset resistance of a large number of toners decrease, and if it exceeds 3.0, in terms of low-temperature fixability, it is slightly lower than that within the range. Inferior.

The condensation type compound has a glass transition point (Tg)
However, the temperature is preferably 50 to 125 ° C., and more preferably 50 to 95 ° C. More preferably, the temperature is 55 to 90 ° C. When the glass transition point is lower than 50 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 125 ° C., the low temperature offset resistance of the toner is lowered.

Acid value of the condensed compound (mgKOH / g)
Is 0.1 to 35, preferably 3 to 35, more preferably 4 to 35, and further preferably 5 to 30. When the acid value is less than 0.1, the rise of the charge amount of the toner is slow and fogging is likely to occur. Acid value is 3
If it exceeds 5, the triboelectrification characteristics of the toner after being left under high temperature and high humidity tend to fluctuate, and the image density tends to fluctuate during continuous sheet feeding. Further, when the acid value of the polar resin exceeds 35, the affinity between the polymers of the polar resin becomes strong, so that the polar resin becomes difficult to dissolve in the polymerizable monomer, and the uniform polymerizable monomer composition is obtained. It takes time to prepare things.

Hydroxyl value of the condensed compound (mgKOH /
g) is 0.2 to 50, preferably 5 to 50, and more preferably 7 to 45. The hydroxyl value is 0.
When it is less than 2, the polar resin is less likely to be localized on the surface of the particles of the polymerizable monomer composition in the aqueous medium, as compared with those in the optimum range. When the hydroxyl value exceeds 50, the charge amount characteristics of the toner after being left under high temperature and high humidity tend to be slightly lower than those in the optimum range, and the image density tends to fluctuate during continuous paper feeding. .

The molecular weight and molecular weight distribution of the condensed compound by GPC are measured by the following methods. The column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was caused to flow through the column at this temperature at a flow rate of 1 ml / min to prepare a THF sample solution of about 100 μm.
l Inject and measure. When measuring the molecular weight of a sample,
The molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko Corporation is used, and it is appropriate to use a standard polystyrene sample of at least about 10 points. is there. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, shodex GPC KF-801, 802, 80 manufactured by Showa Denko KK
Combination of 3,804, 805, 806, 807, 808P Tsk gel G1000H (H
_XL ), G2000H (H _XL ), G3000H (H _XL ),
G4000H (H _XL ), G5000H (H _XL ), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
A combination of rdcolumns may be mentioned.

The sample is manufactured as follows.

The sample is placed in tetrahydrofuran (THF), left to stand for several hours, shaken well and mixed well with THF (until the coalescence of the samples disappears), and then left to stand for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. Then, a filter that passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Maisho Redisk H-25-5 Tosoh Co., Ltd., Excicro Disc 25CR Gelman Science Japan Co., Ltd. can be used) was used. Use as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The glass transition point of the condensed compound is determined by DSC measurement.

In the DSC measurement, it is preferable to use a high-precision internal heat input compensation type differential scanning calorimeter for the measurement principle. For example, DSC-7 manufactured by Perkin Elmer can be used.

The measuring method is ASTM D3418-82.
Carry out according to. For the measurement, a DSC curve measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature is raised and lowered once to take a previous history is used.

The acid value of the condensed compound is determined as follows.

The basic operation complies with JIS-K0070.

Free fatty acid contained in 1 g of sample,
Mg of potassium hydroxide required to neutralize resin acid, etc.
The number is called the acid value, and the test is performed as follows.

(1) Reagent (a) Solvent Ethyl ether-ethyl alcohol mixed solution (1
+1 or 2 + 1) or a benzene-ethyl alcohol mixed solution (1 + 1 or 2 + 1), and these solutions are neutralized with N / 10 potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use. (B) Phenolphthalein solution 1 g of phenolphthalein was added to 100 ml of ethyl alcohol (95 v / v%).
Dissolve in. (C) N / 10 potassium hydroxide-ethyl alcohol solution 7.0 g of potassium hydroxide is dissolved in as little water as possible, ethyl alcohol (95 v / v%) is added to make 1 liter, and the mixture is left for 2 to 3 days and then filtered. JIS K
Perform according to 8006 (basic items regarding titration during reagent content test).

(2) Operation Weigh 1 to 20 g of a sample correctly, add 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator, and shake the sample sufficiently to completely dissolve it. For solid samples, heat on a water bath to dissolve. After cooling, this was titrated with an N / 10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization was determined when the indicator was slightly reddish for 30 seconds.

(3) Calculation Formula The acid value is calculated by the following formula. A = B × f × 5.611 / S A: Acid value B: Amount of N / 10 potassium hydroxide ethyl alcohol solution used (ml) f: Factor of N / 10 potassium hydroxide ethyl alcohol solution S: Sample (g )

The hydroxyl value of the condensed compound is determined as follows.

The basic operation complies with JIS-K0070.

When 1 g of a sample is acetylated by the prescribed method, the mg number of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group is called the hydroxyl value.
Test by operation and formula.

(1) Reagent (a) Acetylating reagent 25 g of acetic anhydride was placed in 100 ml of a volumetric flask and pyridine was added to bring the total volume to 100 ml.
And shake it well. (In some cases, pyridine may be added). Keep the acetylating reagent away from moisture, carbon dioxide and acid vapors and store in amber bottles. (B) Phenolphthalein solution 1 g of phenolphthalein was added to 100 ml of ethyl alcohol (95 v / v%).
Dissolve in. (C) N / 2 potassium hydroxide-ethyl alcohol solution
Dissolve 35 g of potassium hydroxide in as little water as possible,
Ethyl alcohol (95 v / v%) is added to make 1 liter, and the mixture is left for 2 to 3 days and then filtered. JIS K
8006.

(2) Operation Properly weigh 0.5 to 2.0 g of the sample in a round bottom flask, and add the acetylation reagent 5
Correctly add ml. A small funnel is placed on the neck of the flask, and the bottom of about 1 cm is immersed in a glycerin bath at 95 to 100 ° C. for heating. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, cover the base of the neck of the flask with a cardboard disk with a round hole inside. After 1 hour, the flask was taken out of the bath, allowed to cool, 1 ml of water was added from the funnel and shaken to decompose acetic anhydride. To further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and the walls of the funnel and flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol was used as an indicator with the phenolphthalein solution. Titrate with solution. A blank test will be conducted in parallel with the main test. In some cases, a KOH-THF solution may be used as the indicator.

(3) Calculation formula The hydroxyl value is calculated by the following formula. A = (B−C) × f × 28.05 / S + D A: Hydroxyl value B: N / 2 potassium hydroxide in blank test Usage amount of ethyl alcohol solution (ml) C: N / 2 potassium hydroxide in this test Amount of ethyl alcohol solution used (ml) f: N / 2 potassium hydroxide Ethyl alcohol solution factor S: sample (g) D: acid value

Examples of the condensed compound of the present invention include polyester, polycarbonate, phenol resin, epoxy resin, polyamide and cellulose. More preferably, polyester is desired due to the variety of materials.

Examples of the method for producing the condensation compound and the release agent include, for example, a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid and a derivative thereof, an ester group introduction reaction represented by a Michael unreactable reaction, and a carboxylic acid compound. It is produced by a method utilizing a dehydration condensation reaction from an alcohol compound with an alcohol compound, a reaction from an acid halide with an alcohol compound, and a transesterification reaction. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. Then, it may be highly purified by a recrystallization method, a distillation method or the like.

A particularly preferable method for producing the condensation compound and the release agent is a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound in terms of versatility of raw materials and easiness of reaction.

The composition of the condensation type compound used in the present invention will be described below.

The condensation type compound is 45 to 55 mo in all components.
It is preferable that 1% is an alcohol component and 55 to 45 mol% is an acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, the following formula (a)

[0124]

[Chemical 6] (In the formula, R represents an ethylene or propylene group, and x, y
Each represent an integer of 1 or more, and the average value of x + y represents 2 to 10. ) A bisphenol derivative represented by
Or the following formula (b)

[0125]

[Chemical 7] And diols such as the diols represented by

Examples of the divalent carboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride and diphenyl-
PP'-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane-PP'-dicarboxylic acid, benzophenone-
Benzenedicarboxylic acids such as 4,4′-dicarboxylic acid and 1,2-diphenoxyethane-P · P′-dicarboxylic acid or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid Acids, alkyldicarboxylic acids such as triethylenedicarboxylic acid and malonic acid or anhydrides thereof, and further succinic acid or anhydrides thereof substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid,
Examples thereof include unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, or anhydrides thereof.

Particularly preferred in the practice of the present invention, the alcohol component of the condensed compound is a bisphenol derivative represented by the above formula (a), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or an anhydride thereof, Examples thereof include succinic acid, n-dodecenylsuccinic acid, or anhydrides thereof, and dicarboxylic acids such as fumaric acid, maleic acid, and maleic anhydride.

The condensed compound can be obtained by synthesizing a divalent dicarboxylic acid and a divalent diol. In some cases, a trivalent or higher polycarboxylic acid or polyol may be used in a small amount as long as it does not adversely affect the present invention.

Examples of tricarboxylic or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalene tricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylic propane, 1,3-dicarboxyl-2-methyl-methylenecarboxylic propane, tetra (methylenecarboxylic) methane, 1 , 2,7,8-octanetetracarboxylic acid and their anhydrides.

Examples of the trihydric or higher polyols include sorbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4.
-Methanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane,
1,3,5-trihydroxymethylbenzene may be mentioned.

In the present invention, a negative charge control agent other than the above may be blended. The compound is not particularly limited, but examples thereof include salicylic acid-based compounds, naphthoic acid-based compounds, dicarboxylic acid-based compounds, polymer compounds having sulfonic acid in the side chain, and high-molecular compounds having carboxylic acid in the side chain. Molecular type compounds, urea compounds, silicon compounds, currys arenes and the like can be used.

As the release agent, the weight average molecular weight (Mw)
Is 350 to 4000, and the number average molecular weight (Mn) is 200.
To 4000, more preferably M
It is preferable that w is 400 to 3500 and Mn is 250 to 3500. Mw is less than 350 and Mn is 20
When it is less than 0, the blocking resistance of the toner decreases. When Mw exceeds 4000 and Mn exceeds 4000, the crystallinity of the release agent itself is developed and the transparency of the fixed image is lowered.

The molecular weight and molecular weight distribution of the release agent are measured by GPC under the following conditions.

(GPC measurement conditions) Equipment: GPC-150C (Waters Co.) Column: GMH-MT 30 cm 2 series (manufactured by Tosoh Corp.) Temperature: 135 ° C. Solvent: o-dichlorobenzene (added 0.1% ionol) Flow Speed: 1.0 ml / min Reagent: Inject 0.4 ml of 0.15% sample

The molecular weight calibration curve prepared by the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the sample measured under the above conditions. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

The releasing agent preferably has a melting point (the temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 to 120 ° C., more preferably 50 to 90 ° C. As the release agent, a solid wax that is solid at room temperature is preferable, and a solid wax having a melting point of 50 to 90 ° C. is particularly preferable in terms of toner blocking resistance, multi-sheet durability, low temperature fixing property, and offset resistance.

As the wax, paraffin wax,
Polyolefin wax, microcrystalline wax, polymethylene wax such as Fischer-Tropsch wax, amide wax, ketone wax, higher fatty acid, long chain alcohol, ester wax and their graft compounds, derivatives such as block compounds, and these are mentioned. It is preferable that the maximum endothermic peak of the DSC endothermic curve from which the low molecular weight component is removed is sharp. Also, a blend of two or more of these may be used.

Waxes preferably used are linear alkyl alcohols having 15 to 100 carbon atoms,
Examples thereof include linear fatty acids, linear acid amides, linear esters, and montan derivatives. Those in which impurities such as liquid fatty acids have been previously removed from these waxes are also preferable.

Further, the wax preferably used is
Radical polymerization of alkylene under high pressure or polymerization under low pressure using Ziegler catalyst or other catalyst; low molecular weight alkylene polymer; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; when polymerizing alkylene Separation and purification of low-molecular-weight alkylene polymer produced as a by-product; Synthesis obtained from the distillation residue of a hydrocarbon polymer obtained by the Arge process from a synthesis gas consisting of carbon monoxide and hydrogen, or by hydrogenating the distillation residue A polymethylene wax obtained by extracting and fractionating a specific component from a hydrocarbon can be mentioned. An antioxidant may be added to these waxes.

In order to improve the translucency of a fixed image,
Solid ester waxes are preferable, and those having a melting point of 50 to 90 ° C. are particularly preferable.

The ester wax is represented by the following formula (A)
Examples include those formed from the compounds represented by (F) to (F).

[0142]

[Chemical 8] (In the formula, a and b are integers from 0 to 4, and a + b is 4
Is. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference in carbon number between R ₁ and R ₂ is 3 or more. m and n are integers of 0 to 25, and m and n cannot be 0 at the same time. )

[0143]

[Chemical 9] (In the formula, a and b are integers of 0 to 3, and a + b is 1 to
It is 3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference in carbon number between R ₁ and R ₂ is 3 or more. R ₃ is a hydrogen atom or an organic group having 1 or more carbon atoms. However, a + b =
When 2, one of R ₃ is an organic group having 1 or more carbon atoms. k is an integer of 1 to 3. m and n are 0
It is an integer of 25, and m and n cannot be 0 at the same time. )

[0144]

[Chemical 10] (In the formula, R ₁ and R ₃ are organic groups having 6 to 32 carbon atoms, and R ₁ and R ₃ may or may not be the same.
₂ represents an organic group having 1 to 20 carbon atoms. )

[0145]

[Chemical 11]

[0146]

[Chemical 12] (In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. M and n are 0. Is an integer of 25 and m and n
Cannot be 0 at the same time. )

[0147]

[Chemical 13] (In the formula, R ₁ and R ₂ are the same or different and have 15 to 45 carbon atoms.
Shows a hydrocarbon group of. )

Examples of the ester wax as a releasing agent composed of an ester compound include the following.

[0149]

[Chemical 14]

[0150]

[Chemical 15]

When the releasing agent is an ester wax having an ester compound having the above structural formula, it exhibits good transparency and, when contained in the toner particles, exhibits good fixing property. is there. This wax and the polar resin are dissolved in a polymerizable monomer, and then the polymerization reaction of the polymerizable monomer is allowed to proceed in an aqueous medium, so that the toner particles obtained have a large charge amount and an appropriate charge value. It is possible to obtain an excellent toner in which the speed at which the amount of frictional electrification changes is small and the amount of triboelectrification varies little during the durability of many sheets.

When the polymerizable monomer composition is used to directly produce the toner particles in an aqueous medium, it is added in an amount of 1 to 40 parts by mass (more preferably 100 parts by mass of the polymerizable monomer). Is included in the toner particles.

Compared with the dry toner manufacturing method by the melt-kneading and pulverization method, in the toner manufacturing method by the polymerization method, since a large amount of the release agent is easily encapsulated in the toner particles by the polar resin, generally, a large amount of the toner is manufactured. It becomes possible to use a mold agent, which is particularly effective for the offset prevention effect during fixing.

If the amount of the release agent added is less than the lower limit, the offset prevention effect tends to be lowered, and if it exceeds the upper limit, the blocking resistance effect is lowered and the offset resistance effect is liable to be adversely affected. Toner fusion of the developing sleeve is likely to occur, and when toner particles are produced by a polymerization method, toner particles having a wide particle size distribution tend to be produced.

The (SP) value of the releasing agent used in the present invention is preferably in the range of 7.6 to 10.5. S
A release agent having a P value of less than 7.6 has poor compatibility with the polymerizable monomer or binder resin used, and as a result, it is difficult to obtain a good dispersion in the binder resin, and a large number of copies are made. At the time of printing or at the time of printing, the release agent is easily attached to the developing sleeve, and the charge amount of the toner is likely to change. Further, the background fogging and the toner density fluctuation at the time of toner replenishment are likely to occur. When a release agent having an SP value of more than 10.5 is used, blocking of toner particles is likely to occur during long-term storage of the toner. Further, since the compatibility with the binder resin is too good, it is difficult to form a sufficient release layer between the fixing member and the toner binder resin layer during fixing, and the offset phenomenon is likely to occur.

The solubility parameter (SP) value is determined by the method of Fedors (Polym.
Eng. Sci. , 14 (2) 147 (1974)).

The release agent used in the present invention preferably has a melt viscosity at 135 ° C. of 1 to 300 cPs, more preferably 3 to 50 cPs. When the melt viscosity is lower than 1 cPs, when the toner layer is thinly coated on the developing sleeve by a coating blade or the like in the non-magnetic one-component developing method, mechanical contamination causes sleeve contamination. In the two-component developing method, when developing an electrostatic image using carrier particles and toner, the toner is liable to be damaged due to the slipping force between the toner and carrier particles, and the external additive is buried and the toner particles are crushed. Cheap. When the toner has a melt viscosity of more than 300 cPs, when the toner particles are manufactured by using a polymerization method, the viscosity of the polymerizable monomer composition is increased to obtain toner particles having a fine particle size with a sharp particle size distribution. Is not easy.

The melt viscosity of the release agent is VP manufactured by HAAKE.
A method of measuring at -500 using a cone plate type rotor (PK-1) at -500 can be mentioned.

The hardness of the release agent used in the present invention is 0.3.
The range of -5.0 is preferable, and the more preferable Vickers hardness is particularly effective at 0.5-3.0.

A toner containing a releasing agent having a Vickers hardness of less than 0.3 is easily crushed in a cleaning process in copying or printing a large number of sheets and is apt to cause toner fusion on the surface of the photosensitive drum, resulting in an image. Black streaks are likely to occur. When a large number of fixed image samples are piled up and stored, the toner is transferred to the back surface, and the show-through easily occurs.

A toner containing a release agent having a Vickers hardness of more than 5.0 is not preferable because a fixing device used during heat fixing requires an excessive pressing force, and the fixing device needs an excessive strength design. If a fixing device with a normal pressing force is used, the offset resistance tends to decrease, which is not preferable.

The hardness of the release agent can be measured, for example, by a measuring method using a Shimadzu dynamic ultra-micro hardness meter (DUH-200). The measurement conditions were 0.
10 μm at a loading speed of 9.67 mg / sec under a load of 5 g
After the displacement, the Vickers hardness is obtained by holding for 12 seconds and analyzing the dents on the sample. As a sample, a mold having a diameter of 20 mmφ is used, and a previously melted sample is molded into a cylindrical shape having a thickness of 5 mm and used.

From the viewpoint of durability, it is preferable that the additive for the purpose of imparting various characteristics to the toner has a particle diameter of ⅕ or less of the volume average diameter of the toner particles. The particle size of the additive means the average particle size thereof obtained by observing the surface of the toner particles with an electron microscope. As the additives for imparting these characteristics, for example, the following ones are used.

Examples of the fluidity-imparting agent include metal oxide (silicon oxide, aluminum oxide, titanium oxide, etc.) carbon black, carbon fluoride, and the like. Those subjected to a hydrophobic treatment are more preferable.

As the polishing agent, metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, etc.) , Barium sulfate, calcium carbonate, etc.).

Examples of the lubricant include fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.) and the like.

Examples of the charge controllable particles include metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of toner particles.
1-5 parts by weight are used. These additives may be used alone or in combination.

The toner of the present invention can be used as a toner for a non-magnetic one-component developer, and also as a toner for a two-component developer having carrier particles. When a non-magnetic toner is used, there is a method in which a blade or a roller is used, and a developing sleeve is forcibly triboelectrically charged so that the toner adheres to the sleeve to carry the toner.

When used as a two-component type developer, a carrier is used together with the toner of the present invention to be used as a developer. The magnetic carrier is composed of an element consisting of iron, copper, zinc, nickel, cobalt, manganese, and chromium elements alone or in a composite ferrite state. The shape of the magnetic carrier may be spherical, flat or amorphous. Furthermore, the fine structure of the surface state of the magnetic carrier particles (for example, surface irregularity)
Is also preferably controlled. Generally, a method is used in which the above-mentioned inorganic oxide is fired and granulated to generate magnetic carrier core particles in advance and then coated on a resin. From the viewpoint of reducing the load on the toner of the magnetic carrier, after kneading the inorganic oxide and the resin, pulverizing and classifying to obtain a low-density dispersed carrier, and further, directly kneading the inorganic oxide and the monomer It is also possible to use a method of obtaining a spherical spherical magnetic carrier by suspension polymerization in an aqueous medium.

A coated carrier in which the surface of the carrier particles is coated with a resin is particularly preferable. As the method, a method in which a resin is dissolved or suspended in a solvent and applied and then attached to a carrier, or a method in which a resin powder and carrier particles are simply mixed and attached can be applied.

The substance adhered to the surface of the carrier particles varies depending on the toner material, and examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin and polyacid. , Polyvinyl butyral, amino acrylate resin and the like. These are used alone or in plural.

The magnetic properties of the carrier are preferably as follows.
The intensity of magnetization (σ _79.6 ) at _79.6 kA / m (1000 oersted) after magnetic saturation is 3.77.
To 37.7 μWb / cm ³ .
In order to achieve higher image quality, preferably 12.6.
To 31.4 Wb / cm ³ . 37.7
When it is larger than μWb / cm ^3, it becomes difficult to obtain a high-quality toner image. When it is less than 3.77 Wb / cm ³ , carrier adhesion is likely to occur because the magnetic restraining force also decreases.

The carrier shape is SF- which indicates the degree of roundness.
1 is 180 or less, SF-2 indicating the degree of unevenness is 250
The following is preferable. SF-1 and SF-2 are defined by the following formulas and measured by LUZEX III manufactured by Nireco.

[0175]

[Equation 6]

When the toner of the present invention and the magnetic carrier are mixed to prepare a two-component developer, the mixing ratio is 2 to 15% by mass, preferably 4% by mass as the toner concentration in the developer.
Good results are usually obtained when the amount is -13% by mass.

As the black colorant used in the image forming method of the present invention, carbon black, a magnetic substance or the like is used and is not particularly limited. When a magnetic substance is used as the black colorant, unlike the other colorants, the resin 1
40 to 150 parts by weight per 00 parts by weight are generally used.

A charge control agent may be further added to stabilize the triboelectric charging characteristics of the toner. As the charge control agent, a charge control agent which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is preferable. A charge control agent having no polymerization inhibitory property and having no solubilized product in an aqueous medium is particularly preferable.

As specific compounds, salicylic acid compounds, naphthoic acid compounds, dicarboxylic acid compounds, polymer compounds having sulfonic acid in the side chain, polymer compounds having carboxylic acid in the side chain. , Urea compounds, silicon compounds, currys arenes and the like can be used.

However, in the present invention, the addition of the charge control agent is not essential, and when the two-component developing method is used, the triboelectrification with the carrier is used and the non-magnetic one-component blade coating developing method is used. Also, by positively utilizing the triboelectric charging with the blade member or the sleeve member, it is not always necessary to include the charge control agent in the toner particles.

An image forming method to which the toner of the present invention is applicable will be described below with reference to the accompanying drawings.

The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, developing means 17 as shown in FIG. Specifically, while applying an alternating electric field,
A magnetic brush is an electrostatic image carrier (for example, a photoconductor drum) 1
It is preferable to carry out the development in the state of being in contact with No. 3. The distance (SD distance) B between the developer carrying member (developing sleeve) 11 and the photosensitive drum 13 is preferably 100 to 1000 μm in order to prevent carrier adhesion and improve dot reproducibility. If it is narrower than 100 μm, the supply of the developer tends to be insufficient, and the image density becomes low, and 1000 μm
If it exceeds, the magnetic lines of force from the magnet S1 spread, the density of the magnetic brush becomes low, the dot reproducibility becomes poor, or the force for restraining the carrier weakens, and carrier adhesion easily occurs. The toner 21 is sequentially supplied to the developing device, mixed with the carrier by the stirring means 15 and 16, and is conveyed to the developing sleeve 11 including the fixed magnet 14.

The voltage between the peaks of the alternating electric field is 500 to 50.
00V is preferable, the frequency is 500 to 10000 Hz,
The frequency is preferably 500 to 3000 Hz, and can be appropriately selected and used for each process. In this case, the waveform may be triangular wave, rectangular wave, sine wave, or duty.
Various waveforms with different ratios can be selected and used.

If the applied voltage is lower than 500 V, it may be difficult to obtain a sufficient image density, and the fog toner in the non-image area may not be recovered well. 5000V
If it exceeds, the electrostatic image is disturbed via the magnetic brush, which may lead to deterioration in image quality.

By using a two-component type developer having a well-charged toner, the fog removal voltage (Vback)
Can be lowered, and the primary charging of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
The value k depends on the developing system, but is preferably 150 V or less, more preferably 100 V or less.

The contrast potential is preferably 200 V to 500 V so that a sufficient image density can be obtained.

When the frequency is lower than 500 Hz, although it is related to the process speed, charge injection into carriers may occur, which may deteriorate the image quality by adhering carriers or disturbing the latent image. If it exceeds 10000 Hz, the toner cannot follow the electric field and the image quality is likely to deteriorate.

The contact width (developing nip C) of the magnetic brush on the developing sleeve 11 with the photosensitive drum 13 is preferably in order to obtain sufficient image density, excellent dot reproducibility, and development without carrier adhesion. It is to be 3 to 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to satisfactorily satisfy sufficient image density and dot reproducibility.
If the width is larger than mm, the packing of the developer occurs and the operation of the machine is stopped, and it becomes difficult to sufficiently suppress the carrier adhesion. As a method of adjusting the developing nip,
The nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 12 and the developing sleeve 11 or by adjusting the distance B between the developing sleeve 11 and the photosensitive drum 13.

Particularly in the output of a full-color image in which halftone is emphasized, three or more developing devices for magenta, cyan, and yellow are used, and the developer and the developing method of the present invention are used. By combining with a developing system that forms a latent image, there is no influence of the magnetic brush and the latent image is not disturbed, so that it is possible to develop the dot latent image faithfully. Even in the transfer step, a high transfer rate can be achieved by using the toner of the present invention, and therefore high image quality can be achieved in both the halftone portion and the solid portion.

Furthermore, by using the toner of the present invention together with the improvement of the initial image quality, the effect of the present invention can be sufficiently exerted without deterioration of the image quality even when a large number of copies are made.

The toner image on the electrostatic image carrier 13 is transferred onto a transfer material by a transfer means 23 such as a corona charger.
The toner image on the transfer material is fixed by a heat and pressure fixing unit having a heating roller 26 and a pressure roller 25.
The transfer residual toner on the electrostatic image carrier 13 is removed by a cleaning unit 24 such as a cleaning blade.
Removed from. The toner of the present invention has a high transfer efficiency in the transfer step, a small amount of transfer residual toner, and excellent cleaning property, and therefore filming is less likely to occur on the electrostatic image holding member. Further, even when a multi-sheet durability test is performed, the toner of the present invention has less burial of the external additive on the surface of the toner particles than the conventional toner, so that good image quality can be maintained for a long time.

In order to obtain a good full-color image, it is preferable to have a developing device for magenta, cyan, yellow, and black, and to give a tight image by the last development of black. it can.

An example of an image forming apparatus capable of favorably implementing the multi-color or full-color image forming method will be described with reference to FIG.

The color electrophotographic apparatus shown in FIG. 3 includes a transfer material conveying system I provided from the right side of the apparatus main body to a substantially central portion of the apparatus main body, and the transfer material conveying system I provided at a substantially central portion of the apparatus main body. A latent image forming portion II provided in the vicinity of the transfer drum 315 constituting I, and a developing means (that is, a rotary developing device) III arranged in the vicinity of the latent image forming portion II. It is roughly divided into.

The transfer material carrying system I has the following structure. An opening is formed in the right wall (right side in FIG. 3) of the apparatus main body, and transfer material supply trays 302 and 303 that are detachable are provided in the opening so as to partially project outside the machine. Paper feed rollers 304 and 305 are disposed substantially directly above the trays 302 and 303, and these paper feed rollers 304 and 305 and a transfer drum 305 disposed on the left side and rotatable in the direction of arrow A are arranged. A paper feed roller 306 and paper feed guides 307 and 308 are provided so as to be linked. In the vicinity of the outer peripheral surface of the transfer drum 315, the contact rollers 309 are arranged from the upstream side to the upstream side in the rotation direction.
Gripper 310, transfer material separation charger 311, separation claw 3
12 are sequentially arranged.

A transfer charger 313 and a transfer material separating charger 314 are disposed on the inner peripheral side of the transfer drum 315. A transfer sheet (not shown) made of a polymer such as polyvinylidene fluoride is attached to a portion of the transfer drum 315 around which the transfer material is wound, and the transfer material is electrostatically attached on the transfer sheet. It is attached closely to. A conveyor belt means 316 is provided on the upper right side of the transfer drum 315 in proximity to the separation claw 312, and a fixing device 318 is provided at the end (right side) of the conveyor belt means 316 in the transfer material conveying direction. There is. A discharge tray 317 that extends to the outside of the apparatus main body 301 and is detachable from the apparatus main body 301 is disposed further downstream than the fixing device 318 in the transport direction.

Next, the structure of the latent image forming section II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 319 which is a latent image carrier rotatably in the direction of the arrow in FIG. 3 is arranged with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 315. Above the photosensitive drum 319, in the vicinity of the outer peripheral surface thereof, a charger 320 for removing electricity and a cleaning unit 321 from the upstream side to the downstream side in the rotation direction of the photosensitive drum 319.
And a primary charger 323 are sequentially arranged, and an image exposure unit 324 such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 319, and an image exposure reflection unit 325 such as a mirror. It is arranged.

The structure of the rotary developing device III is as follows. A rotatable housing (hereinafter referred to as “rotating body”) 3 is provided at a position facing the outer peripheral surface of the photosensitive drum 319.
26, four types of developing devices are mounted at four positions in the circumferential direction in the rotating body 326.
The electrostatic latent image formed on the outer peripheral surface of is visualized (that is, developed). The above four types of developing devices
Each has a yellow developing device 327Y, a magenta developing device 327M, a cyan developing device 327C, and a black developing device 327BK.

The sequence of the entire image forming apparatus having the above configuration will be described by taking the case of the full color mode as an example. When the photosensitive drum 319 described above rotates in the direction of the arrow in FIG.
Is charged by. In the apparatus of FIG. 3, the peripheral speed of the photosensitive drum 319 (hereinafter, referred to as process speed) is 1
00 mm / sec or more (for example, 130 to 250 mm /
sec). Photosensitive drum 3 by primary charger 323
19 is charged, image exposure is performed by the laser light E modulated by the yellow image signal of the original 328, an electrostatic latent image is formed on the photosensitive drum 319, and development is performed in advance by rotation of the rotating body 326. The electrostatic latent image is developed by the yellow developing device 327Y fixed at the position, and a yellow toner image is formed.

The transfer material conveyed through the paper feed guide 307, the paper feed roller 306, and the paper feed guide 308 is held by the gripper 310 at a predetermined timing, and is brought into contact with the contact roller 309 and the corresponding contact roller. It is electrostatically wound around the transfer drum 315 by the electrodes facing each other. The transfer drum 315 is rotating in the direction of the arrow in FIG.
The yellow toner image formed by 27Y is transferred onto the transfer material by the transfer charger 313 at a portion where the outer peripheral surface of the photosensitive drum 319 and the outer peripheral surface of the transfer drum 315 are in contact with each other. The transfer drum 315 continues to rotate and is ready for transfer of the next color (magenta in FIG. 3).

The photosensitive drum 319 is the charge removing charger 3 described above.
After the charge is removed by 20 and the cleaning means 321 by the cleaning blade cleans it, it is charged again by the primary charger 323, and image exposure is performed by the next magenta image signal to form an electrostatic latent image. The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 319 by imagewise exposure with a magenta image signal to position the magenta developing device 327M at the above-described predetermined developing position and to perform a predetermined operation. Develop with magenta toner. Subsequently, the above-described process is performed for cyan and black, respectively, and when the transfer of the toner images of four colors is completed, the three-color visible image formed on the transfer material is charged by each of the chargers 322 and 314. The gripping of the transfer material by the gripper 310 is released, the transfer material is separated from the transfer drum 315 by the separating claw 312, and the transfer belt 316 fixes the fixing material to the fixing device 3.
Then, it is sent to 18 and fixed by heat and pressure to complete a series of full-color printing sequence, and a required full-color printing image is formed on one surface of the transfer material.

Next, another image forming method will be described more specifically with reference to FIG.

In the apparatus system shown in FIG. 4, the developing devices 44-1, 44-2, 44-3, and 44-4 have a developing agent having a cyan toner, a developing agent having a magenta toner, and a developing agent having a yellow toner, respectively. A developer having a developing agent and black toner is introduced, and the electrostatic charge image formed on the photoconductor 41 is developed by a magnetic brush development system or a non-magnetic one-component development system, and each color toner image is formed on the photoconductor 41. It The photoconductor 41 is a-Se, Cds, Zn.
It is a photosensitive drum or photosensitive belt having a photoconductive insulating material layer such as O ₂ , OPC and a-Si. The photoconductor 41 is rotated in the arrow direction by a driving device (not shown).

As the photosensitive member 41, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer.
It may be a single layer type or a function-separated type photosensitive layer in which the charge transport layer comprises a charge generation layer as a component. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one of preferred examples.

Polycarbonate resin, polyester resin, and acrylic resin are particularly preferable as the binder resin for the organic photosensitive layer because of good transferability and cleaning property, poor cleaning, fusing of toner to the photoreceptor, and filming of external additives. Hard to happen.

In the charging step, there are a method of being in non-contact with the photoconductor 41 using a corona charger, and a method of a contact type using a roller or the like, any of which is used. A contact type as shown in FIG. 4 is preferably used for efficient uniform charging, simplification and low ozone generation.

The charging roller 42 has a basic core bar 42b and a conductive elastic layer 42a formed on the outer periphery of the core bar 42b. The charging roller 42 is pressed against the surface of the photoconductor 41 with a pressing force and is rotated by the rotation of the photoconductor 41.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 4.9 to 490 N / m.
(5 to 500 g / cm), when a DC voltage superimposed with an AC voltage is used, AC voltage = 0.5 to 5 kVp
p, AC frequency = 50 Hz to 5 kHz, DC voltage = ±
The voltage is 0.2 to ± 1.5 kV, and when the DC voltage is used, the DC voltage is ± 0.2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage becomes unnecessary and ozone generation is reduced.

As a material of the charging roller and the charging blade as the contact charging means, conductive rubber is preferable, and a releasing film may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), etc. can be applied.

The toner image on the photosensitive member has a voltage (for example, ±
It is transferred to the intermediate transfer member 45 to which 0.1 to ± 5 kV) is applied. The surface of the photoreceptor after the transfer is cleaned by a cleaning unit 49 having a cleaning blade 48.

The intermediate transfer member 45 comprises a pipe-shaped conductive core 45b and an elastic layer 45 of medium resistance formed on the outer peripheral surface thereof.
It consists of a. The cored bar 45b may be a plastic pipe coated with conductive plating.

The elastic layer 45a of medium resistance is made of silicone rubber, fluorine rubber, chloroprene rubber, urethane rubber,
EPDM (ethylene propylene diene terpolymer)
Conductivity-imparting materials such as carbon black, zinc oxide, tin oxide, and silicon carbide are mixed and dispersed in elastic materials such as to adjust the electric resistance value (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. A solid or foamed fleshy layer.

The intermediate transfer member 45 is arranged in parallel with the photosensitive member 41 so as to be in contact with the lower surface of the photosensitive member 41, and rotates in the counterclockwise direction of the arrow at the same peripheral speed as the photosensitive member 41. To do.

The toner image of the first color formed and carried on the surface of the photoconductor 41 is transferred by the applied transfer bias to the intermediate transfer body 45 while passing through the transfer nip portion where the photoconductor 41 and the intermediate transfer body 45 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 45 by the electric field formed in the nip region.

If necessary, the detachable cleaning means 400 cleans the surface of the intermediate transfer member 45 after the toner image is transferred onto the transfer material. When there is a toner image on the intermediate transfer body, the cleaning unit 400 is separated from the surface of the intermediate transfer body so as not to disturb the toner image.

A transfer means is disposed in parallel with the intermediate transfer body 45 so as to be in contact with the lower surface of the intermediate transfer body 45, and the transfer means 47 is, for example, a transfer roller or a transfer belt. Rotates clockwise at the same peripheral speed as the arrow. The transfer means 47 may be arranged so as to be in direct contact with the intermediate transfer body 45, or a belt or the like may be arranged so as to be in contact between the intermediate transfer body 45 and the transfer means 47.

In the case of the transfer roller, the core metal bar 47b at the center and the conductive elastic layer 47a forming the outer periphery thereof are used as a basic structure.

As the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer member, the voltage applied to the transfer roller can be reduced and a good toner image can be formed on the transfer material. In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer body. Particularly, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer body is 10 times or more than the volume resistivity of the elastic layer of the transfer roller.

The hardness of the intermediate transfer member and the transfer roller is JI.
It is measured according to SK-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to the range of 10 to 40 degrees, while the hardness of the elastic layer of the transfer roller is higher than that of the elastic layer of the intermediate transfer member.
Those having a value of -80 degrees are preferable in order to prevent the transfer material from winding around the intermediate transfer member. When the hardness of the intermediate transfer body and that of the transfer roller are opposite, a recess is formed on the transfer roller side, and the transfer material is likely to be wound around the intermediate transfer body.

The transfer means 47 is rotated at a constant speed or a peripheral speed different from that of the intermediate transfer body 45. The transfer material 46 is conveyed between the intermediate transfer body 45 and the transfer means 47, and at the same time,
The toner image on the intermediate transfer member 45 is transferred to the surface side of the transfer material 46 by applying a bias having a polarity opposite to the triboelectric charge of the toner to the transfer means 47 from the transfer bias means.

The same material as the charging roller can be used as the material of the transfer rotary member, and the preferable transfer process condition is that the contact pressure of the roller is 4.9 to 490 N.
/ M (5 to 500 g / cm), DC voltage is ± 0.2 to
± 10 kV.

For example, the conductive elastic layer 47b of the transfer roller
Is a polyurethane in which a conductive material such as carbon is dispersed, an ethylene-propylene-diene terpolymer (EPDM)
It is made of an elastic body having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the cored bar 47a by a constant voltage power source. The bias condition is ± 0.2 to
± 10 kV is preferable.

Next, the transfer material 46 is conveyed to a fixing device 401 which is basically composed of a heating roller having a heating element such as a halogen heater built therein and an elastic pressure roller pressed against the heating roller by a pressing force, and heated. The toner image is heated and pressed and fixed on the transfer material by passing between the roller and the pressure roller. A method of fixing with a heater through a film may be used.

Next, the one-component developing method will be described. The toner of the present invention can be applied to a one-component developing method such as a non-magnetic one-component developing method.

An example of the developing method in the case of performing the non-magnetic one-component developing will be described with reference to FIG.

Reference numeral 55 is a latent image holder, and the latent image is formed by electrophotographic process means or electrostatic recording means (not shown). A developing sleeve 54 is made of a non-magnetic sleeve such as aluminum or stainless steel. As the developing sleeve 54, a rough tube made of aluminum or stainless steel may be used as it is, but preferably, its surface is uniformly roughened by blowing spherical particles such as glass beads, a mirror-finished one, or a resin coating. Things are good. The toner T is stored in the hopper 51, and is developed by the toner application roller 52 by the developing sleeve (toner carrier).
54. As the toner applying roller 52, a roller made of a foam material such as a porous elastic body (for example, soft polyurethane foam) is preferably used. The roller is rotated with respect to the developing sleeve 54 in a forward or reverse direction at a relative speed which is not 0, and the toner is supplied onto the developing sleeve 54 and the toner (undeveloped toner) after development on the developing sleeve 54 is peeled off. Also do. At this time, the contact width (nip width) of the toner applying roller 52 to the developing sleeve 54 is preferably 2.0 to 10.0 mm in consideration of the balance of toner supply and stripping.
0 to 6.0 mm is more preferable. Although stress is applied to the toner and aggregation of the toner due to deterioration of the toner is increased, or the toner is easily fused and fixed to the developing sleeve 54 and the toner applying roller 52, the toner of the present invention has fluidity and releasability. As it has excellent durability and stability, Fig. 5
It is also preferably used in the developing device shown in. Instead of the toner application roller 52, a brush roller made of resin fiber such as nylon or rayon may be used. The developing method shown in FIG. 5 is extremely effective in a one-component developing method using a non-magnetic one-component toner. The toner supplied onto the developing sleeve 54 is applied in a thin layer and uniformly by the regulating member 53. The toner regulating member 53 is particularly preferably a method in which the surface of the developing sleeve 54 is pressed against the surface of the developing sleeve 54 with an elastic blade or an elastic roller. As the elastic blade or elastic roller, it is preferable to use a material of triboelectrification series suitable for charging the toner to a desired polarity. The regulating member 53 is made of silicone rubber, urethane rubber,
Styrene-butadiene rubber and the like are suitable. further,
An organic resin layer such as polyamide, polyimide, nylon, melamine, melamine crosslinked nylon, phenol resin, fluorine resin, silicone resin, polyester resin, urethane resin, styrene resin, acrylic resin may be provided on the regulating member 53.

The contact pressure between the elastic blade or elastic roller and the developing sleeve 54 is 0.98 to 245 N / m (1-250 g / cm) as a linear pressure in the sleeve generatrix direction.
Preferably 4.9-118 N / m (5-120 g / c
m) is effective, and the contact pressure is 0.98 to 245 N / m.
By adjusting to, it becomes possible to effectively loosen the aggregation of the toner, and it is possible to instantly increase the triboelectric charge amount of the toner. Development sleeve 5 by blade
In a system in which a thin layer of toner is coated on No. 4, especially in the non-magnetic one-component developing method, in order to obtain a sufficient image density, the developing sleeve 54 should be 10
It is rotated at a peripheral speed of 0 to 300%. Preferably 120-
It is rotated at a peripheral speed of 250%.

It is preferable that the thickness of the toner layer on the developing sleeve 54 is made smaller than the opposing gap length between the developing sleeve 54 and the latent image carrier 55, and an alternating electric field is formed in this gap. By applying an alternating electric field or a developing bias in which an alternating electric field is superimposed on a direct current electric field to the developing sleeve 54 by the bias power source 56, the toner can be easily moved from the developing sleeve 54 to the latent image holding member 55, and a higher quality toner can be obtained. Images can be obtained.

Next, the magnetic one-component developing method will be described with reference to FIG.
I will explain based on.

In FIG. 6, the substantially right half peripheral surface of the developing sleeve 63 is constantly in contact with the toner pool in the toner container 64, and the toner near the surface of the developing sleeve 63 is on the developing sleeve surface. And / or electrostatically. When the developing sleeve 63 is driven to rotate, the magnetic toner layer on the sleeve surface passes through the position of the regulating member 66 to be layered as a thin magnetic toner T ₁ having a substantially uniform thickness at each portion. The charging of the magnetic toner is mainly performed by frictional contact between the sleeve surface and the magnetic toner in the toner pool in the vicinity of the developing sleeve 63 as the developing sleeve 63 rotates, and the magnetic toner thin layer surface on the developing sleeve 63 follows the developing sleeve rotation. It rotates to the side of the latent image holding body 67 which does not exist, and passes through the developing area A which is the closest portion between the latent image holding body 67 and the developing sleeve 63. In the course of this passage, the magnetic toner in the thin layer of the magnetic toner on the surface of the developing sleeve 63 flies by the direct current and the alternating electric field due to the direct current and the alternating voltage applied between the latent image carrier 67 and the developing sleeve 63, and the latent image in the developing area A. Between the image carrier 67 surface and the developing sleeve 63 surface (gap α)
Reciprocate. Finally, the magnetic toner on the developing sleeve 63 side is selectively transferred and adhered to the surface of the surface of the latent image holding body 67 according to the potential pattern of the latent image, and toner images T ₂ are sequentially formed.

The developing sleeve surface, through which the magnetic toner has been selectively consumed after passing through the developing area A, is re-rotated to the toner reservoir of the hopper 64 to be re-supplied with the magnetic toner and developed in the developing area A. The surface of the magnetic toner thin layer T _{1 of the} sleeve 63 is transferred and the developing process is repeated.

The regulating member 66 as a toner thinning means used in FIG. 6 is a doctor blade such as a metal blade or a magnetic blade which is arranged with a certain gap from the sleeve. Alternatively, a metal, resin, or ceramic roller may be used instead of the doctor blade. Further, an elastic blade or an elastic roller that comes into elastic contact with the surface of the developing sleeve (toner carrying member) may be used as the toner thinning regulating member.

As the material for forming the elastic blade or elastic roller, silicone rubber, urethane rubber, NBR
A rubber elastic body such as that; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel, steel or phosphor bronze can be used. Further, it may be a complex thereof. Preferably, the sleeve contact portion is made of a rubber elastic body or a resin elastic body.

An example of using an elastic blade is shown in FIG.

The base of the elastic blade 70 on the upper side is fixedly held on the developer container side, and the lower side is flexed in the forward or reverse direction of the developing sleeve 79 against the elasticity of the blade 70. The inner surface side of the blade (or the outer surface side in the opposite direction) is brought into contact with the surface of the sleeve 79 with an appropriate elastic pressure. According to such a device, a thin and dense toner layer can be obtained more stably against environmental changes.

When using an elastic blade, a sleeve,
Although the toner is easily fused on the blade surface, the toner of the present invention is preferably used because it has excellent releasability and stable triboelectrification.

In the case of the magnetic one-component developing method, the blade 70
The contact pressure between the sleeve 79 and the sleeve 79 is 0.98 N / m (1 g / cm) or more, preferably 2.9 to 245 N / m (3 to 250 g / cm), more preferably linear pressure in the sleeve generatrix direction. 4.9-118 N / m (5-120 g / c
m) is effective. The gap α between the latent image holder 78 and the sleeve 79 is set to, for example, 50 to 500 μm. The layer thickness of the magnetic toner layer on the sleeve 79 is most preferably thinner than the gap α between the latent image holding member 78 and the sleeve 79, but in many cases, among the many ears of the magnetic toner forming the magnetic toner layer, The layer thickness of the magnetic toner layer may be regulated so that a part of the magnetic toner layer contacts the latent image carrier 78.

The developing sleeve 79 is a latent image holder 78.
On the other hand, it is rotated at a peripheral speed of 100 to 200%. The alternating bias voltage applied by the bias applying means 76 is peak-to-peak of 0.1 kV or more, preferably 0.2 to 3.0.
It is good to use kV, and more preferably 0.3 to 2.0 kV. The alternating bias frequency is 0.5 to 5.0 kHz,
Preferably 1.0 to 3.0 kHz, more preferably 1.
Used at 5 to 3.0 kHz. The alternating bias waveform is
Waveforms such as rectangular wave, sine wave, sawtooth wave, and triangular wave can be applied. Further, positive and reverse voltages and asymmetrical AC biases with different times can also be used. It is also preferable to superimpose a DC bias.

Each physical property of the toner and the evaluation method of development, fixing and image quality will be described below. The examples described below also follow these evaluation methods.

Measurement of fog The evaluation machine is REFLECTOMETER MODEL TC.
Fog was determined by comparing the whiteness of the transfer paper measured by -6DS (manufactured by Tokyo Denshoku Co., Ltd.) with the whiteness of the transfer paper after printing solid white. It was calculated by the following formula using a blue filter for a yellow toner image and a green filter for a full color image. The smaller the fog value, the better.

Fog (reflectance;%) = (reflectance of standard paper;%)-(reflectance of white solid portion of sample;%)

Measurement procedure (1) After leaving the developing machine filled with toner for a predetermined time in an environment of high temperature and high humidity (30 ° C., 80% RH), the image ratio was measured by using the machine described in Example or Comparative Example. After 5 sheets of 4% image are continuously fed, solid white is output and the fog on the transfer paper at that time is measured. (2) Under the conditions of (1), 6000 sheets of images having an image ratio of 4% are continuously passed, and then solid white is output, and the fog on the transfer paper at that time is measured.

In the case of the two-component development system ○: Absolute value of measured value (1) -measured value (2) is 0.4%
Below ○ △: Absolute value of measured value (1) -measured value (2) is 0.4%
Over 0.8% or less △: Absolute value of measured value (1) -measured value (2) is 0.8%
Over 1.2% or less x: Absolute value of measured value (1) -measured value (2) is 1.2%
Over

Non-magnetic single component ○: Absolute value of measured value (1) -measured value (2) is 1.0%
Below ○ △: Absolute value of measured value (1) -measured value (2) is 1.0%
Over 1.7% or less Δ: Absolute value of measured value (1) -measured value (2) is 1.7%
Over 2.5% or less x: Absolute value of measured value (1) -measured value (2) is 2.5%
Over

The fog measurement values (1) of the toners described in Examples and Comparative Examples were all from 0 to 0.02, and there was no problem in the initial image.

Measurement of Toner Scattering After the image was formed under the following conditions, the toner scattering around the developing machine was visually confirmed.

Measurement Procedure (1) After leaving the developing machine filled with toner in a high temperature and high humidity environment for a predetermined time, five machines were continuously run with 4% image ratio using the machine described in Example or Comparative Example. After printing on paper, visually check the toner scattering around the developing machine. (2) Under the conditions of (1), 6000 sheets of images with a ratio of 4% are continuously fed, and then the toner scattering around the developing machine is visually confirmed. Based on the results of the visual observation of (1) and (2), the following level division was performed. ○: Clean without toner scattering. ○ △: Toner scatters a little but is clean. Δ: Toner scattered and slightly dirty. X: Toner is scattered and dirty.

Measurement of Transferability After the image was formed under the following conditions, the transferability was judged by the number of traces of transfer failure.

Measurement Procedure (1) After leaving the developing machine filled with toner in a high temperature and high humidity environment for a predetermined time, five images of 4% image ratio were continuously transferred using the machine described in the examples or comparative examples. After printing on paper, all solids were output and judged by the number of traces of transfer failure in the A3 image. (2) Under the conditions of (1), 6000 sheets of images having an image ratio of 4% were continuously fed, and then all solids were output, and judgment was made by the number of traces of transfer failure in the A3 image. Based on the results of the visual observation of (1) and (2), the following levels were classified. ◯: Number of traces of transfer failure is 0 to 4 ○ Δ: Number of traces of transfer failure is 5 to 9 Δ: Number of traces of transfer failure is 10 to 14 ×: Number of traces of transfer failure is 15 or more

Measurement of Transparency The transparency of the transparency sheet image is evaluated as follows.

Using the machine described in the examples or comparative examples, yellow toner having gradation is not fixed on the transparency sheet (CG3700: 3M) under normal temperature and normal humidity (20 ° C., 60% RH) environment. I got an image. An external fixing device in which the surface of the fixing roller is a fluororesin (no oil application function; roller diameter 40 mm)
At a fixing temperature of 180 ° C and a process speed of 40 mm /
A fixed image was obtained in sec. The transmittance of the obtained fixed image was measured at a portion having an image density of 0.5 to 0.6 mg / cm ² . The transmittance is measured by the Shimadzu self-spectrophotometer UV2200.
(Manufactured by Shimadzu Corporation) was used for the measurement. Then, the transmittance of the transparency sheet alone is set to 100%, and 6
The transmittance at the maximum absorption wavelength at 00 nm was measured.

The following criteria were used for evaluation. ○: transmittance is 80% or more B: Transmittance is 65% or more and less than 80% Δ: Transmittance of 50% or more and less than 65% X: The transmittance is less than 50%

For measuring the color space of the projected image of the full-color image, the obtained full-color image is used as a transmission image with an overhead projector (OHP: 9550 manufactured by 3M), and the image projected on a white wall is used for spectral radiance. Measured with a total (PR650 manufactured by Photo Research Co.), and C
IELAB color system of lightness L ^*, a ^* representing the degree of red or green, was obtained a three-dimensional volume of the b ^* indicating a degree of yellow or blue. A larger number means a wider color space, and a smaller number means a narrower color space. The unit is Lab cubed.

Measurement of Fixability Under a high-temperature and high-humidity environment, with the machine described in the examples or comparative examples, an image pattern in which the secondary colors of red and blue can be simultaneously taken (a frame of 3 cm × 3 cm is defined as the central portion of A4) 100 sheets of the patterns output to the four corners) were continuously passed, and the fixing state of the image on the 100th sheet was visually observed. As the transfer material, Xerox 105 g / m ² A4 paper was used.
The toner loading amount of the next color was set to 1.0 to 1.2 mg / cm ² . Further, as a fixing condition, the surface of the fixing roller is made of a fluororesin (no oil coating function; roller diameter 40).
mm), fixing temperature 180 ° C, process speed 140m
A fixed image was obtained at m / sec. ◯: Level with no blister-shaped fixing failure. Δ: Level from 1 to 5 small blisters with a diameter of less than 2 mm. Δ: 6 to 10 small blisters with a diameter of less than 2 mm.
Level x: There are 11 or more small blisters with a diameter of less than 2 mm or a level with large blisters with a diameter of 2 mm or more.

[0257]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention in any way.
The number of parts in the following formulation is part by mass unless otherwise specified.

<Example 1> Ion-exchanged water 1 in a reaction vessel
To 0000 parts, 100 parts of 0.1 M Na ₃ PO ₄ aqueous solution and 85 parts of 1 M HCl aqueous solution were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 60 parts of 1.0M-CaCl ₂ aqueous solution was added all at once while stirring at 12000 rpm to prepare an aqueous medium containing a calcium phosphate salt having a pH of 6.5. did. -Styrene 80 parts-n-butyl acrylate 20 parts-Yellow colorant 7 parts-Compound of hydroxycarboxylic acid and Al 0.8 parts (counter ion K ⁺ )-Condensation compound 10 parts ([saturated polyester (terephthalic acid- Propylene oxide-modified bisphenol A, acid value 9, peak molecular weight 6000)]-ester wax (release agent No. 5) 15 parts-crosslinking agent (divinylbenzene) 0.25 parts

The above materials were kept warm in a separate container at 65 ° C.
Using a K-type homomixer (made by Tokushu Kika Kogyo), 12
It was uniformly dissolved and decomposed at 000 rpm. 4 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in this to prepare a polymerizable monomer composition.

The above polymerizable monomer composition was put into the above aqueous medium in a reaction vessel, and the mixture was stirred at 65 ° C. under N ₂ purge with a TK homomixer at 10,000 rpm for 10 minutes to prepare a polymerizable monomer. The body composition was granulated. After that, while stirring with a paddle stirring blade, at 65 ° C for 6 hours, and then at 85 ° C.
The temperature was raised to 0 ° C., the reaction was performed for 9 hours, and then distillation was performed at 85 ° C.

After the completion of the polymerization reaction, the reaction vessel was cooled, hydrochloric acid was added to dissolve the calcium phosphate salt, and the mixture was filtered, washed with water and dried to obtain yellow toner particles. When the cross section of the yellow toner particles was observed by TEM,
As shown in FIG. 1, it was confirmed that the release agent was well encapsulated in the outer shell resin.

100 parts of the obtained yellow toner particles and B
A negative triboelectrically-chargeable yellow toner was obtained by mixing with 1.5 parts of hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the ET method. The circle-equivalent number average diameter D ₁ of the obtained yellow toner was 4.8 μm.

To 5 parts of this yellow toner, 95 parts of an acrylic-coated ferrite carrier was mixed to prepare a developer, and a full-color copying machine (creative processor 660, equipped with an intermediate transfer member as shown in FIG. 4).
Using a modified machine manufactured by Canon Inc., an image output test of the replenishment type yellow toner was conducted.

Table 1 shows the formulation of the toner, Table 2 shows the physical properties of the toner, and Table 3 shows the measurement results.

Example 2 A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the aqueous medium of pH = 10.2 was prepared without adding the 1M-HCl aqueous solution. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Examples 3 to 5> A yellow toner was manufactured by performing the same experiment as in Example 1 except that shown in Table 1.
Table 3 shows the toner physical properties, and Table 3 shows the toner measurement results.

Example 6 A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the granulation temperature was 73 ° C. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Examples 7 to 11> The same experiment as in Example 1 was carried out except that the toner formulations shown in Table 1 were used to produce a yellow toner. Table 2 shows the toner physical properties, and Table 3 shows the toner measurement results.

<Example 12> 10% of 1M-HCl aqueous solution was added.
A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the content was changed to 5 parts and the aqueous medium was pH = 5.6. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

Example 13 The amount of 0.1 M Na ₃ PO ₄ aqueous solution to 60 parts, the amount of 1.0 M CaCl ₂ aqueous solution to 35 parts, TK type homomixer (made by Tokushu Kika Kogyo). A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the rotation speed was changed to 7,000 rpm. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Comparative Examples 1 and 2> A yellow toner was manufactured by performing the same experiment as in Example 1 except for the toner formulations shown in Table 1. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

Comparative Example 3 Polyester resin obtained by condensing propoxylated bisphenol and fumaric acid 100 parts Yellow coloring agent 6 parts Compound of hydroxycarboxylic acid and Al 4 parts (counter ion K ⁺ ) Ester wax (release agent No. 5) 2 parts

Other than this, the toner prescription shown in Table 1 was used.
The mixture was sufficiently premixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, cooled, roughly crushed to about 1 to 2 mm with a hammer mill, and then finely crushed with a fine crusher by an air jet system. Further classification was carried out to obtain yellow toner particles. The circle-equivalent number average diameter D _{1 of the} obtained yellow toner was 5.6 μm. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Comparative Example 4> A yellow toner was manufactured in the same manner as in Comparative Example 3 except that the yellow toner of Comparative Example 3 was subjected to wet heating sphering treatment at Tg or higher. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Comparative Example 5> A 1 M-HCl aqueous solution was not added, and an aqueous medium having a pH of 10.2 was prepared, and the hydroxycarboxylic acid and the Al compound were changed to the aromatic hydroxycarboxylic acid and the Al compound. A yellow toner was manufactured in the same manner as in Example 1 except that the toner formulations shown in Table 1 were used. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

<Comparative Example 6> Hydroxycarboxylic acid and Al
A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the compound was changed to an aromatic hydroxycarboxylic acid and a Ti compound. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

Comparative Example 7 A yellow toner was manufactured according to the toner formulation shown in Table 1 in the same manner as in Example 1 except that the granulation temperature was 55 ° C. and the polymerization initiator was 2 parts. Table 2 shows toner physical properties, and Table 3 shows toner measurement results.

[0278]

[Table 1]

[0279]

[Table 2]

[0280]

[Table 3]

Example 14 A yellow toner, a magenta toner, a cyan toner or a black toner was manufactured in the same manner as in Example 1 except that the toner formulations shown in Table 4 were obtained, and the toner physical properties shown in Table 5 were obtained. . A toner was prepared from the obtained four color toners in the same manner as in Example 1 and the two-component developing method shown in FIG. 2 was used to carry out the full-color copying machine (creative processor 660) equipped with the intermediate transfer member shown in FIG. , Canon) and a full-color image output test was performed. The measurement results are shown in Table 6, respectively.

Example 15 Except for the toner formulations shown in Table 4, the same experiment as in Example 1 was carried out to produce yellow toner, magenta toner, cyan toner or black toner, and the toner physical properties shown in Table 5 were obtained. . The obtained four-color toners were subjected to full-color processing using a non-magnetic single-component developing method shown in FIG. 5 by a modified full-color copying machine (Creative Processor 660, manufactured by Canon) equipped with the intermediate transfer body shown in FIG. An image output test was performed. The measurement results are shown in Table 6.

Comparative Example 8 A yellow toner, a magenta toner, a cyan toner, or a black toner was manufactured in the same manner as in Example 1 except that the toner formulations shown in Table 4 were obtained, and the toner physical properties shown in Table 5 were obtained. . A toner was prepared from the obtained four color toners in the same manner as in Example 1 and the two-component developing method shown in FIG. 2 was used to carry out the full-color copying machine (creative processor 660) equipped with the intermediate transfer member shown in FIG. , Canon) and a full-color image output test was performed. The measurement results are shown in Table 6, respectively.

Comparative Example 10 A yellow toner, a magenta toner, a cyan toner or a black toner was manufactured in the same manner as in Example 1 except that the toner formulations shown in Table 4 were obtained, and the toner physical properties shown in Table 5 were obtained. . The obtained four-color toners were processed by the non-magnetic one-component developing method shown in FIG. 5 into a full-color copying machine (creative processor 660, manufactured by Canon) equipped with the intermediate transfer member shown in FIG. An image output test was performed. The measurement results are shown in Table 6.

[0285]

[Table 4]

[0286]

[Table 5]

[0287]

[Table 6]

[0288]

According to the present invention, the transparency of the yellow projected image of the OHP (overhead projector) is excellent, the fog and toner scattering on the transfer material at high temperature and high humidity are small, and the transferability is good. It is possible to provide a toner and an image forming method that have excellent fixability in superimposing more than one color, have a wide color space of a full-color projected image of OHP, and have excellent transparency.

[Brief description of drawings]

FIG. 1 is a schematic view of a cross section of toner particles in which a release agent is encapsulated in an outer shell resin.

FIG. 2 is a schematic view of a developing device to which the toner of the present invention can be applied.

FIG. 3 is a schematic diagram for explaining a full-color or multi-color image forming method.

FIG. 4 is a schematic diagram of an image forming method using an intermediate transfer member.

FIG. 5 is a schematic view showing a non-magnetic one-component developing device.

FIG. 6 is a schematic view showing a magnetic one-component developing device.

FIG. 7 is a schematic view showing a magnetic one-component developing device.

[Explanation of symbols]

11 Anti-developer carrier (developing sleeve) 12 Developer regulating member 13 Electrostatic charge image carrier (photosensitive drum) 25 pressure roller 26 heating roller

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Katsuyuki Nonaka             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Hiroaki Kawakami             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Satoshi Handa             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yuji Moriki             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA06 AA15 AA21 CA21                       CA25 DA02 EA05 EA06 EA07

Claims (25)

[Claims] 1. At least a binder resin, a colorant, a release agent,
And a hydroxycarboxylic acid represented by the following formula (I) and 2
A toner containing a compound with a trivalent or trivalent metal, wherein the colorant is C.I. I. Pigment Yellow 1
80 alone or C.I. I. Pigment Yell
ow 180 and C.I. I. Solvent Yellow
w 162, the soluble component of tetrahydrofuran (THF) in the toner has a weight average molecular weight of 10,000 to 600,000 in gel permeation chromatography (GPC), and is measured by a flow type particle image measuring device. A toner having an average circularity of 0.920 to 0.995 and a circularity standard deviation of less than 0.040. [Chemical 1] (In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a nitro group,
It represents a substituent selected from the group consisting of a cyano group, an amino group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. ) 2. The C.I. of the colorant. I. Solvent Y
ellow 162 / C. I. Pigment Yel
The toner according to claim 1, wherein the ratio of low 180 is 0 to 3.0. 3. The C.I. of the colorant. I. Solvent Y
ellow 162 / C. I. Pigment Yel
The toner according to claim 1, wherein the ratio of low 180 is 0 to 2.0. 4. The toner according to claim 1, wherein the coloring agent is contained in an amount of 1 to 15 parts by mass based on 100 parts by mass of the binder resin. 5. The toner according to claim 1, wherein the colorant is contained in an amount of 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. 6. A circle-equivalent number average diameter D ₁ (μm) in a number-based circle-equivalent diameter-circularity scattergram measured by a flow-type particle image measuring device for toner is 2 to 10 μm
The toner according to any one of claims 1 to 5, wherein m is m. 7. Tetrahydrofuran (TH) of the toner
7. The weight average molecular weight of the soluble component of F) in gel permeation chromatography (GPC) is 50,000 to 400,000.
The toner according to any one of 1. 8. The toner according to claim 1, wherein the releasing agent is contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the binder resin. 9. The toner according to claim 1, wherein the releasing agent is contained in an amount of 3 to 30 parts by mass based on 100 parts by mass of the binder resin. 10. The toner according to claim 1, wherein the average circularity of the toner is 0.965 to 0.990 and the standard deviation of circularity is less than 0.035. 11. A toner equivalent number of toner particles having a circularity of less than 0.950 in a number-based circle equivalent diameter-circularity scattergram measured by the flow type particle image measuring device is 15 number% or less. Claim 1 characterized by the above-mentioned.
11. The toner according to any one of 1 to 10. 12. A full-color image forming method using a toner containing at least a binder resin, a colorant, a release agent, and a compound of a hydroxycarboxylic acid represented by the following formula (I) and a divalent or trivalent metal. The yellow colorant in the toner is C.I. I. Pigmen
t Yellow 180 alone or C.I. I. Pi
gment Yellow 180 and C.I. I. Sol
Vent Yellow 162 in combination, the soluble component of tetrahydrofuran (THF) in the toner has a weight average molecular weight in gel permeation chromatography (GPC) of 10,000 to 600,000, and is measured by a flow type particle image measuring device. The full-color image forming method, wherein the toner has an average circularity of 0.920 to 0.995 and a circularity standard deviation of less than 0.040. [Chemical 2] (In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a nitro group,
It represents a substituent selected from the group consisting of a cyano group, an amino group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. ) 13. The full-color image forming method according to claim 12, wherein the magenta colorant in the toner is a quinacridone type and / or an azo type, and the cyan colorant is a phthalocyanine type. 14. The colorant according to claim 12, wherein the magenta colorant is a quinacridone solid solution pigment, and the cyan colorant is copper phthalocyanine.
The method for forming a full-color image according to item 3. 15. The magenta colorant in the colorant is C.I. I. Pigment Red 122 and C.I. I.
Pigment Violet 19 or C.I. I. P
igment Red 202 and C.I. I. Pigme
nt Violet 19 solid solution pigment, wherein the cyan colorant is C.I. I. Pigment Blue 15; The full-color image forming method according to claim 12, wherein the full-color image forming method is Pigment Blue 15. 16. A colorant for the yellow toner, comprising C.I. I. Solvent Yellow 162 / C.
I. Pigment Yellow 180 ratio is 0
To 3.0, characterized in that
The method for forming a full-color image according to any one of 1. 17. A colorant for the yellow toner, comprising C.I. I. Solvent Yellow 162 / C.
I. Pigment Yellow 180 ratio is 0
To 2.0.
The method for forming a full-color image according to any one of 1. 18. The full-color image forming method according to claim 12, wherein the coloring agent is contained in an amount of 1 to 15 parts by mass per 100 parts by mass of the binder resin. 19. The full-color image forming method according to claim 12, wherein the coloring agent is contained in an amount of 2 to 10 parts by mass per 100 parts by mass of the binder resin. 20. An equivalent circle number average diameter D ₁ (μm) in a number-based circle equivalent diameter-circularity scattergram of the toner measured by a flow type particle image measuring device is 2 to 10.
20. The full-color image forming method according to claim 12, wherein the full-color image forming method is μm. 21. Tetrahydrofuran (TH
21. The full-color image forming method according to claim 12, wherein the soluble component of F) has a weight average molecular weight of 50,000 to 400,000 in gel permeation chromatography (GPC). 22. The full-color image forming method according to claim 12, wherein the releasing agent is contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the binder resin. 23. The full-color image forming method according to claim 12, wherein the release agent is contained in an amount of 3 to 30 parts by mass based on 100 parts by mass of the binder resin. 24. The full-color image according to claim 12, wherein the toner has an average circularity of 0.965 to 0.990 and a circularity standard deviation of less than 0.035. Forming method. 25. In the number equivalent circle-based diameter-circularity scattergram of the toner measured by the flow type particle image measuring device, 15% or less of the toner particles have a circularity of less than 0.950. 25. The full-color image forming method according to claim 12, wherein.