JP2002123041A - Yellow toner and developer for yellow - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow toner having good light resistance, OHP (overhead projector) transparency, transferability and fixability, ensuring stable image density even in the evaluation of a printed-out image and free of fog. SOLUTION: The yellow toner contains at least a bonding resin, a yellow colorant and an oxycarboxylic acid. The yellow colorant is C.I.Pigment Yellow 93 and/or C.I.Solvent Yellow 162 (described in the fourth edition of the Color Index). When the content of the yellow colorant is represented by A (mg) and the mass of the oxycarboxylic acid extracted from 1 g yellow toner with an aqueous sodium hydroxide solution having 0.1 mol/l concentration is represented by B (mg), the expressions A/B=5-1,000 and B=0.10-3.50 are satisfied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a yellow toner and a yellow developer used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

[0002]

2. Description of the Related Art In recent years, digital full-color copying machines and printers have been put into practical use, and high-quality images excellent in color reproducibility without color unevenness as well as developing power and gradation have been obtained.

[0003] With the recent price reduction of computer equipment intended for personal users, full-color video communication has become widespread in the visual world of video information transmission mechanisms. Under such circumstances, full-color image forming apparatuses such as printers and copiers, which are one of output means, are rapidly becoming full-colored, mainly in the low-grade machine market, and full-color images are more familiar to personal users. It is becoming something.

As such full-color output devices, there are generally many methods such as a thermal transfer system, an ink ribbon system, and an ink jet system, but an electrophotographic system occupies the majority as a whole.

In general, in the electrophotographic system, an electric latent image is formed on a photoreceptor by various means using a photoconductive substance,
Next, the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper.
The image is fixed by heating and pressing or by a solvent vapor to obtain a fixed image.

In particular, in the case of full color, three chromatic toners of three primary colors of a yellow toner, a magenta toner, and a cyan toner, or a black toner is added thereto.
Color reproduction is performed using color toners. For example, an electrostatic latent image is formed on the photoconductive layer by passing light from a document through a color separation light passing filter that has a complementary color relationship with the color of the toner. Next, the color toner is held on the support through a development step and a transfer step. Next, the above-described steps are sequentially performed a plurality of times, and while the registration is being performed, the color toners are superimposed on the same support, and a final full-color image is obtained by fixing.

In recent years, demands for higher image quality and higher definition in full-color images have been increasing. For a personal user who has been considered for printing, full-color copy images are not yet at a satisfactory level, and they want a level closer to printing and a level closer to photography. That is, realization of uniformity of a solid image over a wide image area of a copied image, uniformity of a halftone image, and a wide dynamic range from high density to low density is desired, and development of a toner capable of outputting high image density is desired. Has become an urgent need.

Further, when a transfer material such as OHP (overhead transparency) is used, transparency has become important. When internal scattering of transmitted light occurs in the toner layer to be formed, the transmittance is reduced. Therefore, in consideration of this point, it is considered that the dispersibility of the pigment greatly affects the transmittance.

Regarding the dispersibility of the colorant, see, for example, JP-A-61-117565 and JP-A-61-1560.
Japanese Patent Laid-Open No. 54-34978 discloses a method in which a binder resin, a colorant and a charge control agent are dissolved in a solvent in advance and the solvent is removed to obtain a toner. A method (flashing method) of charging a press cake with a kneader and dispersing a heat-kneaded pigment in a resin is disclosed.

These methods certainly produce a certain effect of improving the dispersibility of the colorant, and can improve the coloring power. However, it has been found that some conventional methods are inadequate to meet the further demands of the market.

For example, the method using a solvent as disclosed in JP-A-61-117565 and JP-A-61-156054 has a problem that the production cost is high.
Further, in the flushing method as disclosed in JP-A-5-34978, the resin and the colorant are sufficiently heated and kneaded below the boiling point of water, and the colorant in the aqueous press cake needs to be transferred into the resin. The physical properties of the resin are limited.

In the case of producing a toner by a polymerization method, for example, a method in which a colorant is grafted and used as disclosed in Japanese Patent Application Laid-Open No.
No. 648, a method using a colorant treated with a coupling agent-based dispersant, and Japanese Unexamined Patent Publication No. 64-59242, a method using a colorant treated with a surfactant-based dispersant. Has been proposed.

These methods certainly produce a certain effect of improving the dispersibility of the colorant, and can improve the coloring power. However, in the case of producing toner particles having a small particle size in an aqueous medium, the conventional method has not been sufficient.

For example, in the method of using after grafting as disclosed in Japanese Patent Application Laid-Open No. 56-116044, the production cost is high, and due to the influence of the monomer polymer and the like used for the grafting, the granulation property is low. Somewhat insufficient.

When a colorant treated with a coupling agent / surfactant-based dispersant as in JP-A-58-7648 or JP-A-64-59242 is used,
The treatment agent deteriorates the charging characteristics and makes fogging easy.

Further, the dispersed state of the pigment greatly affects the triboelectric charging characteristics of the toner. JP 8
Japanese Patent Publication No. 209017 discloses the use of a pigment having a pigment having a surface area improved from a needle shape to a cubic shape. No effect on photographic properties is suggested.

Further, in JP-A-6-230607, the content of the yellow colorant in the toner is 75% by mass or less.
It is described that another yellow colorant different from the proposed yellow colorant can be used in combination, and a charge control agent that does not affect the color tone of the toner is also used. However, the publication does not actually manufacture a toner using different types of colorants in combination in the examples, and the effect of the combined use is not clear.

Further, as a method of using a dye having excellent dispersibility and transparency as a colorant, JP-A-50-46333, JP-A-4-291360 and JP-A-4-24.
A method for improving the transparency by a method of dyeing particles as disclosed in Japanese Patent No. 3267 and a method of using an oil-soluble dye as disclosed in Japanese Patent Application Laid-Open No. 62-295069 have been proposed.

In the method using these dyes, it is very easy to disperse the colorant, but it has been found that there are some problems.

One is that the hiding power of the dye is extremely small as compared with that of the pigment, so that it is sufficient for an image to obtain transmitted light using a transparent sheet for an overhead projector, but requires reflected light. An image is disadvantageous in that it is easily affected by a transfer material.

That is, when an image is obtained using a transfer material such as paper, the effect of the paper formation causes 1) the color of the image changes depending on the quality of the paper, and 2) the toner paste such as a highlight portion. In the case of an image having a small amount, the boundary between the image and the white background is difficult to be clear, resulting in a problem such as a poor image. This effect is remarkable in a yellow toner having a high brightness.

As described above, it is the present situation that an OHP (overhead projector) having a sufficiently satisfactory performance has not yet been obtained.

In particular, when the particle size of the toner is reduced, there arises a problem that the charging characteristics are more likely to be affected by the uneven distribution of the colorant.

Accordingly, there is a demand for a toner in which the colorant in each color toner is more well-dispersed than before, and has a well-balanced hue and spectral reflection characteristics and a sufficient saturation.

Further, when the particle size of the toner is reduced, light is more liable to be scattered, so that the chromaticity, lightness, density, etc. of the image change, and a color configuration different from that of the conventional technique is required. Also occurs.

Further, with the spread of printers in recent years, when an image is obtained in accordance with a new user orientation, that is, an image tailored to the tendency to prefer an image similar to other matte printed matter such as photoengraving printing, the above-mentioned problem occurs. It will be noticeable.

In recent years, as a further application of electrophotographic technology, there has been a movement to retransfer an image to steel or cloth, but such a processed product is more likely to be used outdoors because of its use. Heat resistance and light resistance are required.

Conventional color pigments for yellow toner include C.I. I. Pigment Yellow 12/13 /
Azo pigments represented by C.17 and the like; I. Pig
In general, monoazo pigments such as, for example, Ment Yellow 74/97/98 are used. As pigments having excellent light resistance, C.I. I. PigmentYe
Pigments typified by low 93/94/95/180 and the like, and benzimidazole azo pigments described in JP-A-8-262799 have been disclosed. Japanese Patent Application Laid-Open No. 2000-162824 discloses that a specific pigment and dye are combined.

However, as a colorant which satisfies the above-mentioned needs and can further improve the image characteristics and the charging characteristics, a colorant which has not yet been sufficiently satisfactory has not been obtained.

In addition, a stable charge amount and OH
For the purpose of improving the transparency of the P sheet, a toner containing a hydroxycarboxylic acid derivative has been proposed (JP-A-7-84409, JP-A-8-262800). However, C.I. I. disperse Ye
low 12/14, C.I. I. solvent Ye
low 21/77/114, C.I. I. disper
In combination with a yellow colorant using, for example, se Yellow 164, environmental stability of charge amount / image density, transparency of a sheet with an OHP (overhead projector), or light resistance and transferability are not always satisfactory. It was not something.

On the other hand, output devices such as copiers and laser beam printers using the above-described electrophotographic process use a large amount of image information in recent years due to cost reductions and advances in digital technology, so that high-quality images more faithful to originals can be obtained. Is required. In particular, in the copying of print photographs, catalogs, maps, and the like, it is required to reproduce extremely finely and faithfully without being crushed or interrupted even to a minute portion.

In the course of such a technique, the characteristics of the developer are such that the toner does not scatter to the latent image under the processes of development, transfer, and fixation while maintaining high chargeability of the toner itself. Further, it is desired that the developed toner be transferred onto transfer paper in a form close to 100%.

[0033]

SUMMARY OF THE INVENTION An object of the present invention is to provide a yellow toner and a yellow developer which can solve the above problems.

That is, an object of the present invention is to provide a yellow toner and a yellow developer which are stable in charge amount and image density even when printing out a large number of sheets, have no fog, and have a small environmental difference.

It is a further object of the present invention to provide a yellow toner and a yellow developer having excellent light fastness.

It is a further object of the present invention to provide a yellow toner and a yellow developer having good transferability.

It is a further object of the present invention to provide a yellow toner and a yellow developer having good sheet transparency in an OHP (overhead projector).

A further object of the present invention is to provide a yellow toner and a yellow developer which are well matched with a fixing device.

[0039]

The present invention relates to a yellow toner containing at least a binder resin, a yellow colorant and an oxycarboxylic acid, wherein the yellow colorant is CI Pigment Yellow 93. And / or CI Solvent Yellow 162
(Each according to the name described in the color index 4th edition), the content of the yellow colorant is A (mg), and oxycarboxylic acid extracted from 1 g of the yellow toner with a 0.1 mol / l sodium hydroxide aqueous solution. Where A / B = 5 to 1000 B = 0.10 to 3.50, where B is the mass of B (mg).

The present invention also relates to a yellow developer having the above-structured yellow toner and carrier.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventors have found that
The content of the colorant in 1 g of the yellow toner is represented by A (mg),
A / B = 5 to 1000 B = 0.10 to 3.50, where B (mg) is the weight of oxycarboxylic acid extracted from 1 g of the yellow toner with an aqueous 0.1 mol / liter sodium hydroxide solution. It has been found that the above problems can be improved by satisfying In particular, oxycarboxylic acid represented by (1) or (2) described below and C.I. I. Pigment Yellow
w 93 and / or C.I. I. Solvent Yellow
ow 162 is effective for the combination.

First, the toner of the present invention contains at least a binder resin, a yellow colorant and an oxycarboxylic acid, and satisfies B = 0.10 to 3.50, whereby the triboelectric charge amount and the charging speed are reduced. It is possible to suppress the decrease. When the value of B is less than 0.10, a sufficient amount of charge cannot be given to the toner, and the toner tends to fog. When the value of B is less than 3.50, the charge amount of the toner is too high, and the charge distribution becomes broad. Therefore, fogging is also easy.

The amount of oxycarboxylic acid B (hereinafter referred to as "oxycarboxylic acid amount B") extracted from the toner with a 0.1 mol / liter aqueous sodium hydroxide solution is determined by the amount of oxycarboxylic acid present on the surface of the toner particles. The present inventors believe that this value has a great effect on the charge amount of the toner.

Further, C.I. I. Pi
gment Yellow 93 and C.I. I. Solv
Since ent Yellow 162 itself has a high charge amount, the relationship between the colorant content A and B contained in 1 g of the yellow toner satisfies the following relational expression A / B = 5-1000. Accordingly, even when a large number of printouts are performed, the charge amount and the image density are stable, and it is possible to reduce environmental differences.

If the value of A / B is less than 5, the light resistance of the colorant is reduced by oxycarboxylic acid, and if it exceeds 1,000, the charge amount of the colorant becomes dominant, so that the charge amount increases. Too long, which hinders matching with the image forming apparatus.

The oxycarboxylic acid maintains a stable charge amount and also functions as a pigment dispersion stabilizer. I. Pigment Yellow
It also has the effect of dispersing w 93 in a good state and improving the transparency of the OHP sheet.

The amount of oxycarboxylic acid to be added depends on the binder resin 10
It is preferable to use 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, per 0 parts by mass. When the amount of the oxycarboxylic acid is less than 0.005 parts by mass, the dispersibility of the colorant is insufficient, the transparency is poor, and the toner cannot be provided with a sufficient charge amount. If the amount exceeds 20 parts by mass, problems such as a decrease in light resistance due to oxycarboxylic acid and an excessive increase in the charge amount of the toner occur.

When the toner of the present invention is a polymerization method, an oxycarboxylic acid may be contained in the aqueous phase or / and the oily addition.

The oxycarboxylic acid according to the present invention includes
Known compounds can be used, but compounds represented by the following formulas (1) and (2) are preferably used from the viewpoint of the charge imparting ability.

[0050]

Embedded image [In the above formula (1), (A) is selected from the following group, and X ₁
Represents a hydrogen atom, a sodium atom, a potassium atom, ammonium or an aliphatic ammonium. ]

[0051]

Embedded image

[0052]

Embedded image [In the above formula (2), X ₂ represents a hydrogen atom, a sodium atom, a potassium atom, ammonium, or an aliphatic ammonium, and R ₄ represents a C _{1 to} C ₂₂ alkyl group or alkenyl group, or an aryl group. , R ₅ are hydrogen atoms, C ₁ -C
_{22 represents} an alkyl group, an alkenyl group, an aryl group, and an alkoxy group. ]

Among the oxycarboxylic acids represented by the above formulas (1) and (2), those preferably used in the present invention are oxycarboxylic acids having an aromatic ring,
Monoalkyl aromatic oxycarboxylic acids or dialkyl aromatic oxycarboxylic acids are mentioned. In particular, salicylic acid, alkylsalicylic acid typified by di-tert-butylsalicylic acid and 5-tert-octylsalicylic acid, hydroxynaphthoic acid, benzylic acid, etc. are preferably used in the present invention because they can be easily fixed to the toner surface.

The following are typical examples of typical compounds.

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

In the present invention, the amount B of oxycarboxylic acid extracted with a 0.1 mol / liter aqueous sodium hydroxide solution was measured by the following method.

50 ml of a 0.1 mol / l sodium hydroxide aqueous solution to which 0.04 g of contaminone N (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a dispersant was prepared in a container, and 1 g of the toner was weighed and added thereto. , 5 using a stirrer
Stir at 0 rpm and disperse uniformly. After the dispersion treatment for 3 hours, the membrane filter (pore size: 0.
45 μm), and the absorption spectrum of the obtained filtrate is measured with a spectrophotometer, and the difference between the maximum value of the maximum absorption peak exhibited by oxycarboxylic acid and the baseline is determined. At this time, as shown in FIG. 1, for example, when the heights of the right and left base lines of the peak are different from each other in the absorption spectrum of oxycarboxylic acid, the absorbance is determined by the following procedure. A tangent ab is drawn for the maximum absorption peak exhibited by oxycarboxylic acid. A line passing through the peak apex A and parallel to the y-axis and a tangent a
Let B be the intersection with b. The values of the absorbance at A and B are A 'and B', respectively. The absorbance is determined from A'-B '.

From the obtained results, the amount B of oxycarboxylic acid was calculated using a predetermined calibration curve. The absorption spectrum of oxycarboxylic acid appears, for example, in the range of 280 to 350 nm.

The coloring agent used in the present invention includes C.I. I.
Solvent Yellow 162 and / or C.I.
I. Pigment Yellow 93 is preferred.

Further, C.I. I. Solvent
Yellow 162: C.I. I. Pigment Y
The ratio of yellow 93 is preferably 25:75 to 75:25. If the ratio is out of the above range, bright colors cannot be obtained.

The colorant is used in an amount of 1 per 100 parts by mass of the binder resin.
The content is preferably from 1 to 15 parts by mass, more preferably from 2 to 10 parts by mass. When the amount is less than 1 part by mass, the amount of consumed toner increases in order to obtain a sufficient image density. If the amount exceeds 15 parts by mass, the effect of the charge amount of the colorant greatly acts, and the charge amount of the toner becomes too high.

The colorant may be surface-treated.

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

When the toner of the present invention has a good circularity distribution, in particular, it is possible to prevent the toner remaining on the transfer from increasing and the fusion of the toner to the toner carrier due to the decrease in the developing efficiency.

In the toner of the present invention, a flow type particle image measurement
Circle equivalent diameter based on the number of toners measured by the device-circularity
In the scattergram, the circle-equivalent number average of the toner
Diameter D ₁Is 2 to 10 μm, and the average circle of the toner is
The formality is 0.920 ~ 0.995 and the circularity standard deviation is
Precisely adjust the toner particle shape to less than 0.040
By controlling, it is contained in the toner in a specific state
The effect of adding oxycarboxylic acid
Become. Although the reason for this is not always clear,
The inventors believe that the toner particle shape is controlled as described above.
Makes the toner surface shape more uniform.
Therefore, oxycarboxylic acid works efficiently.
Charge characteristics without deteriorating toner powder characteristics.
And that the transferability can be improved satisfactorily.
I have. Also, the shape of the toner particles must satisfy the above conditions.
Color toner of the same content in each toner particle
Effect due to the coloring agent
Will also be uniform. As a result, developability and transferability
Has been improved in a well-balanced manner, and
Matching is significantly improved.

That is, the toner equivalent circle diameter average diameter D _{1 is set} to 2
By reducing the particle size to 10 μm or less, the reproducibility of the contour portion of the image, particularly the development of a character image or a line pattern, becomes good. Further, the average circularity of the circularity frequency distribution of the toner is 0.920 to 0.995, preferably 0.9 to 0.995.
50 to 0.995, more preferably 0.975 to 0.9
By setting the ratio to 95, the transferability of a toner having a small particle size, which has been difficult in the past, is greatly improved, and the developing ability for a low-potential latent image is also significantly improved. In particular, the above tendency is very effective when developing a digital minute spot latent image or when forming a full-color image in which an intermediate transfer body is used to perform multiple transfers, and the matching with the image forming apparatus is also good. It becomes something.

Further, the toner of the present invention has a circularity standard deviation of the circularity frequency distribution of the toner of less than 0.040, preferably less than 0.035, more preferably 0.015 or more.
By setting it to be less than 035, the problem relating to the developability can be significantly improved.

The circularity frequency distribution has an average circularity of 0.
By setting the toner content of less than 950 to 15% or less, the development efficiency in image formation becomes a sufficient level, and the image formation becomes good.

As described above, the control of the toner average circularity, the circularity standard deviation, and the number of toners having a circularity of less than 0.950 is performed in the polymerization method from the granulation step to the polymerization step in the toner production method by the polymerization method. Of aqueous dispersion medium
H is possible.

The circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles. In the present invention, the flow type particle image analyzer FP manufactured by Toa Medical Electronics Co., Ltd.
The particle shape is measured using IA-1000, and the circularity is determined by the following equation. Further, as shown by the following equation, the value obtained by dividing the total sum of the measured circularities of all the particles by the total number of particles is defined as the average circularity.

[0075]

(Equation 1)

[0076]

(Equation 2)

Here, the “particle projection area” is the area of the binarized toner particle image, and is “the peripheral length of the particle image projection”.
Is defined as the length of the contour obtained by connecting the edge points of the toner particle image.

The measuring device “FPIA-1000” used in the present invention calculates the circularity of each particle,
In calculating the average circularity and the circularity standard deviation, the circularity was determined to be 0.400 to 1.0 depending on the circularity obtained.
00 is divided into 61 divided ranges at intervals of 0.010 from 0.400 to less than 0.410, 0.410 to less than 0.420 ... 0.990 to less than 1.000, and 1.000. Is used to calculate the average circularity and the circularity standard deviation using the median value and the frequency.

Each value of the average circularity and the standard deviation of the circularity calculated by this calculation method, and each value of the average circularity and the standard deviation of the circularity calculated by the above-described calculation formula directly using the circularity of each particle. Is very small and practically negligible, and in the present invention, each of the above-described methods is used for data handling reasons such as shortening the calculation time and simplifying the calculation formula. Utilizing the concept of a calculation formula that directly uses the circularity of particles, such a calculation method partially modified is used.

The degree of circularity in the present invention is an index indicating the degree of irregularity of particles, and is 1. if the particles are perfectly spherical.
000, and the degree of circularity becomes smaller as the surface shape becomes more complicated.

The circle equivalent diameter is a value defined as circle equivalent diameter = (particle projection area / π) ^1/2 × 2, and circle equivalent number average diameter (D ₁ ) is based on the number basis. The average value of the circle-equivalent diameter of the toner is represented by the following equation, where di is the particle size (center value) at the dividing point i of the particle size distribution, and fi is the frequency.

[0082]

(Equation 3)

The dividing points of the particle size distribution in the present invention are as shown in the following table.

[0084]

[Table 1]

As a specific measuring method, 10 ml of ion-exchanged water from which impurity solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added thereto as a dispersant. Then, 0.02 g of a measurement sample is further added and uniformly dispersed. As a means for dispersing, a dispersant for measurement using an ultrasonic disperser “UH-50 type” (manufactured by SMT Co.) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is used. And At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not become 40 ° C. or higher.

The binder resin of the toner used in the toner of the present invention has a weight average molecular weight of 30,000 to 600,000 in gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component, and a THF-insoluble component of 0. It is preferably about 60%. More preferably, the weight average molecular weight is from 50,000 to 4
By adjusting the value to 00000, desirable characteristics can be imparted to the toner.

That is, when the insoluble component of THF is less than 3% by mass, the toner becomes too soft, and the fixing property is deteriorated due to an offset phenomenon at the time of fixing. When the insoluble component of THF exceeds 60% by mass, OHP tends to have poor transparency.

If the weight-average molecular weight is less than 30,000, the toner is too soft, causing a decrease in fixability due to the offset phenomenon.
If the ratio exceeds the range, the toner is too hard, so that the fixing property also decreases.

In the present invention, the THF-insoluble content of the binder resin indicates the mass ratio of the resin component insoluble in THF (tetrahydrofuran) of the resin composition in the toner particles, and the resin composition containing a crosslinking component Is a measure of the degree of cross-linking, but even if the THF-insoluble content is 0% by mass, it does not necessarily mean that cross-linking is not performed. The THF-insoluble matter is defined by a value measured as follows.

That is, when the developer is a non-magnetic toner, the pigment content and the like are measured in advance by a known method, and when the developer is a magnetic toner, the pigment and the magnetic material content are measured in advance. Next, a fixed amount of 0.5 to 1.0 g of the developer is weighed (W
₁ g), put in a cylindrical filter paper (No. 86R, manufactured by Toyo Roshi Kaisha), and run through a Soxhlet extractor.
Extraction was performed for 20 hours using 200 ml, the soluble components extracted by the solvent were evaporated, and then dried at 100 ° C. for several hours under vacuum, and the amount of the THF-soluble resin component was weighed (W _2).
g). Then, among pigments and magnetic substances contained in the fixed amount of the developer, the mass of a component soluble in THF is W ₃ g, T ₃
Assuming that the mass of the component insoluble in HF is W ₄ g, the THF insoluble content in the resin composition is calculated according to the following equation.

[0091]

(Equation 4)

In the present invention, the molecular weight distributions of the binder resin component and the polar resin described below are measured by GPC (gel permeation chromatography) under the following conditions. The sample was previously dispersed in the solvent for 12 hours or more.
After dissolving, a solution filtered with a solvent-resistant membrane filter (pore diameter: 0.45 μm) is used.

<GPC Measurement Conditions for Binder Resin Component and Polar Resin Component> Apparatus: GPC-150C (manufactured by Waters) Column: Shodex GPC KF-801 to 80
7, 808P (manufactured by Showa Denko KK), or TSKgel G1000H (XL) to G700
8 stations of 0H (XL) and TSKguardcolumn (manufactured by Tosoh Corporation) Temperature: 40 ° C Solvent: THF Flow rate: 1.0 ml / min Sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by mass
Injection Measurement is performed under the above conditions, and the molecular weight of the sample is calculated by using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample and converting to polystyrene using a conversion formula derived from the Mark-Houwink viscosity formula.

Examples of the wax component that can be used in the present invention include aliphatic hydrocarbons, aliphatic metal salts, higher fatty acids, fatty acid esters or partially saponified products thereof, silicone oil, and various waxes. Among them,
Aliphatic hydrocarbons having a weight average molecular weight of about 1,000 to 10,000 are preferred. Specifically, one or a combination of two or more of low-molecular-weight polypropylene, low-molecular-weight polyethylene, paraffin wax, and a low-molecular-weight olefin polymer composed of olefin units having 4 or more carbon atoms is suitable.

The wax component is used in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. In the suspension polymerization method, the toner of the present invention is dissolved in a monomer and polymerized.

The resin having a polar group may be used alone or in combination of two or more, and preferably 1 to 25 parts by mass, more preferably 2.25 parts by mass, based on 100 parts by mass of the binder resin in the toner particles. It is added so as to be 5 to 15 parts by mass. If the amount is less than 1 part by mass, the function as an upper layer of the toner particles is deteriorated.

The amount of oxycarboxylic acid near the toner surface can be controlled by the amount of the polar resin added. That is, the content of oxycarboxylic acid near the surface can be adjusted by adjusting the amount of addition. Further, it is possible to prevent the colorant from being exposed on the toner surface and adversely affecting the chargeability of the toner.

The resin having a polar group has an acid value of 5 to 2
0 mgKOH / g, more preferably 8 to 15 mgKOH
/ G. When the acid value is less than 5 mgKOH / g, it becomes difficult to contain oxycarboxylic acid near the toner surface, and when the acid value exceeds 20 mgKOH / g, the content of oxycarboxylic acid near the toner surface is large. In either case, it is difficult to produce a toner satisfying the above conditions.

Further, in the suspension polymerization method, when a polar resin is added in the dispersion step, the surface of the toner is covered with the added polar resin due to the polarity of the aqueous dispersion medium. The content of oxycarboxylic acid near the toner surface can be controlled by the thickness of the surface layer. Further, it is also possible to impart a charging property by the polar resin on the toner surface.

The resin having a polar group used in the present invention is preferably a polyester resin or a derivative thereof.
The composition of a typical polyester resin is as follows.

As the alcohol component of the polyester resin, ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, pentanediol, hexanediol, neopentyl glycol, hydrogenated bisphenol A, or the following formula (I) Bisphenol derivatives represented by the following formulas, and diols represented by the following formula (II).

[0102]

Embedded image (Wherein, R represents an ethylene or propylene group, x, y
Represents an integer of 1 or more, respectively, and the average value of x + y represents 2 to 10. )

[0103]

Embedded image

The acid component includes benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof And the like. Also, trimellitic acid,
Polyvalent carboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof can also be used.

The alcohol component of the polyester resin is particularly preferably a bisphenol derivative represented by the above formula (I), and the acid component is phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid or anhydrides thereof. Can be

The method for producing the toner of the present invention will be described in detail later. When suspension polymerization is used, for example, tricalcium phosphate, magnesium phosphate, or the like may be used as an inorganic oxide as a dispersant to be used. Aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate,
Examples include bentonite, silica, alumina, a magnetic material, and ferrite. As the organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like can be used by dispersing them in an aqueous phase. It is preferable to use 0.2 to 10.0 parts by mass of these dispersants based on 100 parts by mass of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound may be produced under high-speed stirring in a dispersion medium. it can.

In order to make these dispersants finer, a surfactant in an amount of 0.001 to 0.1 part by mass may be used in combination with 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic, or cationic surfactants can be used. For example, sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate,
Examples thereof include sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

In the present invention, when preparing an aqueous dispersion medium in which the poorly water-soluble inorganic dispersant as described above is dispersed, a commercially available dispersant may be used as it is, but it may be finely dispersed. In order to obtain dispersant particles having an appropriate particle size, the dispersion may be prepared by generating the above-mentioned hardly water-soluble inorganic dispersant in a solvent such as water under high-speed stirring. For example, in the case of tricalcium phosphate, a dispersant suitable for suspension polymerization can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

Next, the polymerizable monomer composition used in producing the toner of the present invention will be described. The polymerizable monomer composition is at least a polymerizable vinyl monomer, a colorant, a charge control agent, and the oxycarboxylic acid described above, preferably, in addition to this, a wax component, and It is prepared by dissolving and mixing various additives accordingly.

As the polymerizable vinyl monomer used in this case, specifically, a vinyl polymerizable monomer capable of radical polymerization with a styrene monomer is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p Styrene derivatives such as -methoxystyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, ter
t-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 acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Acrylic polymerizable monomers such as;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-
Methacrylic polymerizable monomers such as ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, benzoic acid Vinyl esters such as vinyl acid and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 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- (methacryloxy diethoxy) phenyl) propane, 2,
2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether, and the like.

In the present invention, a styrene monomer and
The above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. Polyfunctional polymerizable monomers can also be used as crosslinking agents.

As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator are used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-
Azo compounds such as dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylper Oxycarbonate,
Decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide And peroxide initiators such as methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide.

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

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like may be further added and used. These additives may be added to the polymerizable monomer composition in advance, or may be added as needed during the polymerization reaction.

As the charge control agent used in the present invention, a charge control agent which has a particularly fast charging speed and can stably maintain a constant charge amount is preferable. Further, a charge control agent which does not inhibit polymerization during production of the toner and has no solubilized substance in an aqueous dispersion medium is preferable. Specifically, as the negative charge control agent, a metal compound of an aromatic carboxylic acid such as salicylic acid, naphthoic acid, and dicarboxylic acid; a polymer compound having a sulfonic acid or carboxylic acid group in a side chain; a boron compound; A silicon compound; Examples of the positive charge control agent include a quaternary ammonium salt; a polymer compound having the quaternary ammonium salt in a side chain; a guanidine compound; and an imidazole compound. The amount of these charge control agents to be contained in the polymerizable monomer was 0.2 to 100 parts by mass of the polymerizable monomer.
It is preferable to use in the range of 10 to 10 parts by mass.

In the present invention, in order to produce toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase migration property of the colorant. If necessary, the surface of the colorant may be subjected to a hydrophobic treatment with a substance that does not inhibit polymerization to modify the surface. In particular, attention must be paid to the use of dyes and carbon blacks because many of them have polymerization inhibitory properties.

As a preferable method for treating the dye, there is a method in which a polymerizable monomer is polymerized in the presence of the dye in advance. The obtained colored polymer is added to the polymerizable monomer composition. The carbon black may be treated with a substance (for example, organosiloxane or the like) that reacts with the surface functional group of the carbon black, in addition to the treatment similar to the above-described dye.

Further, in the present invention, a magnetic toner can be obtained by incorporating a magnetic material. In this case, the magnetic material can also serve as a colorant. The magnetic material that can be used in the present invention is magnetite, hematite,
Iron oxides such as ferrite; metals such as iron, cobalt, nickel, or these metals, and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys with metals such as manganese, selenium, titanium, tungsten, and vanadium, and compounds thereof.

Further, as these magnetic materials used in the present invention, more preferably, surface-modified magnetic materials are used. In particular, it is preferable to use one that has been subjected to a hydrophobic treatment with a surface modifier that does not inhibit polymerization. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.

Further, as these magnetic materials, those having an average diameter of 1 μm or less, preferably 0.1 to 1 μm may be used. 795.8 kA / m (10 k
Coercive force (H)
c) 1.6 to 24 kA / m (20 to 300 Oe), and saturation magnetization (σr) of 2 to 20 Am ² / kg
It is preferable to use

As the other additives to be added to the polymerizable monomer composition, for example, the following ones are used for the purpose of imparting various properties. As the lubricant, a fluororesin powder (polyvinylidene fluoride, polytetrafluoroethylene, etc.) and a fatty acid metal salt (zinc stearate, calcium stearate, etc.) are preferably used.
As the charge control particles, metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, and the like) are preferably used. These additives are used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymerizable vinyl monomer. These additives are used alone or as a mixture.

When the toner of the present invention is used as a developer, an inorganic fine powder having a specific surface area of preferably not less than 30 m ² / g by nitrogen adsorption measured by a BET method is preferably added to 100 parts by mass of toner particles. It is preferable to contain it in the range of 0.5 to 5 parts by mass. As described above, by preparing the developer using the inorganic fine powder having a controlled specific surface area, the developer interacts with the oxycarboxylic acid present on the toner surface, thereby controlling the adsorption of moisture to the toner particles. This is because the effect is more remarkably performed, and the effect of suppressing a decrease in the triboelectric charge amount and the charging speed is increased. In addition, the interaction between the oxycarboxylic acid and the inorganic fine powder increases the effect of preventing oxycarboxylic acid from contaminating the toner carrier and the like. Further, by suppressing the degree of aggregation of the toner, the contact state between the toner particles and the inorganic fine powder is suppressed, and the above-described excellent effect is maintained even in continuous copying.

[0125] As described above, a preferable range of the specific surface area of the inorganic fine powder used in the present invention, but is 30 m ² / g or more, more preferably 50 to 400 m ² / g.
That is, in the case of an inorganic fine powder having a specific surface area of less than 30 m ² / g,
It is difficult to control the degree of aggregation of the toner, and when oxycarboxylic acid is present on the surface of the toner particles, the site of interaction with the compound is saturated, and the effect of preventing contamination of the toner carrier is reduced. It will be smaller. When the specific surface area exceeds 400 m ² / g, the degree of aggregation of the toner may change over time because the inorganic powder is embedded in the surface of the toner particles during continuous copying. The specific surface area is
According to the BET method, specific surface area measuring device Auto Soap 1
Nitrogen gas was adsorbed on the surface of the sample by using (manufactured by Yuasa Ionics Co., Ltd.) and calculated by using the BET multipoint method.

When the amount of the inorganic fine powder to be externally added is less than 0.5 parts by mass, it is difficult to control the degree of aggregation of the toner. May pollute the body.

[0127] The inorganic fine powder used in the present invention includes:
If necessary, for the purpose of hydrophobicity and charge control, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, other organic silicon compounds, organic titanium compounds, etc. It is possible and preferable to use a treating agent or a combination of various treating agents. In particular, in order to maintain a high charge amount and achieve low consumption and high transfer rate, it is preferable that the inorganic fine powder be treated with at least silicone oil.

In the toner of the present invention, other additives such as lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder and polyvinylidene fluoride powder within a range that does not substantially adversely affect the toner. Fluidizing agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents; or conductivity imparting agents such as carbon black powder, zinc oxide powder and tin oxide powder; or organic fine particles and inorganic fine particles of opposite polarity Fine particles can be used in a small amount as a developability improver.

The method for producing the toner of the present invention may be either a pulverized toner or a polymerized toner, and more preferably a polymerized toner.

In the production method of the toner of the present invention, in the case of the polymerization method, at least a polymerizable vinyl monomer, a colorant, an oxycarboxylic acid and a polymerizable initiator, and if necessary, a polar resin and a wax component are added. This polymerizable monomer composition is dispersed in an aqueous dispersion medium, and the particles of the polymer composition are granulated in the aqueous dispersion medium, and the polymerizable vinyl monomer in the particles of the polymer composition is dispersed. The monomer is polymerized to form toner particles. Specifically, the toner is obtained by a suspension polymerization method performed under the conditions described below.

That is, it comprises a polymerizable vinyl monomer, a colorant, a charge control agent, a polymerization initiator, and an oxycarboxylic acid, and, if necessary, a wax component, a polar resin, and other additives added as required. A polymerizable monomer composition is prepared, and the polymerizable monomer composition is charged into an aqueous dispersion medium containing a dispersant prepared in advance, and the polymerizable monomer composition is stirred at high speed. Is dispersed and granulated. At this time, the oxycarboxylic acid and the colorant are included in the toner by adjusting the pH of the aqueous medium to an acidic range of 4.5 to 8.5.
Further, by performing granulation in an acidic region, a toner having a good average circularity can be obtained. When the pH during granulation is less than 4.5, the dispersant does not work stably, and when the pH exceeds 8.5, the oxycarboxylic acid in the aqueous medium elutes from the toner surface,
The dispersant does not work well and the average circularity of the toner decreases. While performing stirring to such an extent that sedimentation of the obtained granulated particles is prevented, depending on the forming material of the monomer composition in the granulated particles, polymerization is performed by setting the range of 40 ° C to 95 ° C. Do.
In the polymerization step or the vapor deposition step, the pH in the aqueous medium is adjusted to 9.0
Need to readjust to 13.0. Thereby, the oxycarboxylic acid is well dispersed in the toner. p
When H is adjusted to less than 9.0, or when readjustment is not performed, the dispersion concentration of oxycarboxylic acid near the surface of the toner decreases, and when the pH exceeds 13.0, the oxycarboxylic acid decreases from the toner surface. May be eluted. Also,
After completion of the granulation and / or reaction, the temperature may be raised, or a part of the aqueous dispersion medium may be distilled off. After performing the polymerization reaction as described above, the generated toner particles are collected by washing / filtration and dried to obtain toner particles.

Although the toner of the present invention can exhibit excellent performance as a one-component developer, it can be used as a two-component developer mixed with a magnetic carrier described below.
Further excellent images can be provided.

The carrier used in the present invention is 10 ¹¹ -1.
0 ¹⁵ Ω · cm and a high resistance carrier, preferably a magnetic fine particle dispersed resin carrier (hereinafter “magnetic resin carrier”)
). By using a high-resistance carrier, it is possible to minimize the adverse effect of the chargeability of the colorant of the present invention and maintain good chargeability. The resistance value of the carrier of the present invention, 10 of less than ¹¹ Omega · cm, the charge is easy fog can not provide sufficient charge quantity to the toner tends to leak, become charge-up tends exceeds 10 ¹⁵ Omega · cm Since the distribution of the charge amount of the toner becomes broad, the toner tends to fog.

In particular, it is formed of composite particles whose particle surfaces are treated with a specific coupling agent, and is obtained by dispersing inorganic compound particles.

The inorganic compound particle powder constituting the composite particles in the present invention may be any as long as it does not dissolve in water or is not altered or denatured by water. As the magnetic inorganic compound particle powder, magnetite particle powder, maghemite particle powder, particle powder obtained by coating or containing cobalt on these, barium, strontium or barium-strontium-containing magnetoplumbite-type ferrite particles powder, manganese, nickel Various magnetic particles such as spinel-type ferrite particles containing one or more selected from zinc, lithium, magnesium and the like can be used. Nonmagnetic inorganic compound particles include hematite particles, ferric hydroxide particles, titanium oxide particles, silica particles, talc particles, alumina particles, barium sulfate particles, barium carbonate particles, and cadmium yellow. Particle powder, calcium carbonate particle powder,
Zinc white particles can be used.

As the particle form of the inorganic compound particles, any form such as a cube, a polyhedron, a sphere, a needle, and a plate can be used. The average particle size may be a particle smaller than the average particle size of the composite particles, and may be 0.0
2 to 5.0 μm, especially 0.02 μm for the magnetic particle powder (a).
Non-magnetic particle powder (b) is 0.05-5 μm,
1.5a <b is preferred.

The mixing ratio of the magnetic particles and the non-magnetic particles is preferably such that the magnetic particles contain at least 30% by mass.

The whole or a part of the inorganic compound particle powder is treated with a lipophilic treatment agent.

Examples of the lipophilic treatment agent include one or more functional groups selected from epoxy groups, amino groups, mercapto groups, organic acid groups, ester groups, ketone groups, halogenated alkyl groups and aldehyde groups. An organic compound having a group or a mixture thereof can be used, and any of them can achieve the object of the present invention. Of these, a coupling agent containing a functional group is preferable, and a silane coupling agent is particularly preferable. Further, as a preferable functional group, an epoxy group, an amino group, and a mercapto group are preferable in that the particle size distribution of the carrier is sharp, and further, the epoxy group is hardly affected by temperature and humidity, and has a charge imparting ability of the carrier. Is preferred in that it is stable.

Examples of the organic compound having an epoxy group include:
Epichlorohydrin, glycidol, styrene-glycidyl (meth) acrylate copolymer and the like.

Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) trimethoxysilane and the like. is there.

Examples of the organic compound having an amino group include ethylenediamine, diethylenetriamine, and styrene-
And dimethylaminoethyl (meth) acrylate copolymer.

Examples of silane coupling agents having an amino group include γ-aminopropyltrimethoxysilane, N
-Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

Examples of the titanium-based coupling agent having an amino group include isopropyl tri (N-aminoethyl) titanate.

Examples of the organic compound having a mercapto group include mercaptoethanol and mercaptopropionic acid.

Examples of the silane coupling agent having a mercapto group include γ-mercaptopropyltrimethoxysilane.

Examples of the organic compound having an organic acid group include oleic acid, stearic acid, styrene-acrylic acid and the like.

Examples of the organic compound having an ester group include:
Examples include ethyl stearate and styrene-methyl methacrylate.

Examples of the organic compound having a ketone group include cyclohexanone, acetophenone, and methyl ethyl ketone resin.

Examples of the organic compound having a halogenated alkyl group include chlorohexadecane and chlorodecane.

Examples of the organic compound having an aldehyde group include propionaldehyde and benzaldehyde.

The amount of the lipophilic treatment agent in the present invention is preferably 0.1 to 5.0% by mass based on the weight of the inorganic compound particles.

When the amount is less than 0.1% by mass, it is difficult to adhere the resin coating to the surface of the composite particles, and the content of the inorganic compound particles is high due to insufficient lipophilic treatment. Composite particles cannot be obtained.

When the content exceeds 5.0% by mass, the resin coating can be brought into close contact with the surface of the composite particles, but the formed composite particles agglomerate, and the particle size of the composite particles cannot be controlled. It becomes difficult.

The binder resin constituting the composite particles in the present invention is preferably a thermosetting resin.

Examples of thermosetting resins include phenolic resins, epoxy resins, polyamide resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, xylene resins, acetoguanamine resins, furan resins, silicone resins, and polyimide resins. , Urethane resin, etc.
These resins may be used alone or in combination of two or more, but it is preferable that the resin contains at least a phenol resin.

In the present invention, the ratio of the binder resin and the inorganic compound particles constituting the composite particles is 1 to 20% by mass of the binder resin and 80 to 99% of the inorganic compound particles.
It is preferable that the content is mass%.

In the magnetic carrier according to the present invention, the surface of the composite particles is coated with a coupling agent having one or more functional groups selected from an epoxy group, an amino group and a mercapto group. By coating with a coupling agent, it is possible to sufficiently withstand the stress of the developer accompanying the printout. When a coupling agent having the above functional group is used, matching with the oxycarboxylic acid on the toner surface is excellent, and a good charge amount can be maintained. It is preferable to select a functional group contained in the coupling agent that reacts with a functional group contained in the lipophilic treatment agent treating the inorganic compound particle powder in the composite particles.

For example, when the functional group contained in the lipophilic treatment agent obtained by treating the inorganic compound particle powder is an amino group, the epoxy resin or mercapto group may be selected as the functional group contained in the coating coupling agent. Good. When the functional group contained in the lipophilic treatment agent obtained by treating the inorganic compound particle powder is an epoxy group, the functional group contained in the coating coupling agent is preferably an amino group.

When the functional group contained in the coating coupling agent and the functional group contained in the lipophilic treatment agent obtained by treating the inorganic compound particle powder are the same amino group, for example, a weak hydrogen bond is formed. Doing so has some effect, but its binding strength is weak.

The reaction of these functional groups is as follows, taking a silane coupling agent as an example.

[0162]

Embedded image

The type of the coating coupling agent may be any of the above-mentioned various coupling agents used in the lipophilic treatment of the inorganic compound particle powder. Is preferred in that it does not impair.

The coating amount of the coupling agent is preferably 0.001 to 5.0% by mass based on the composite particles. 0.0
When the amount is less than 01% by mass, it is difficult to bring the coating of the coupling agent into close contact with the surface of the composite particles, and there is a problem in durability of the charge amount. If it exceeds 5.0% by mass, the coating of the coupling agent can be brought into close contact with the surface of the composite particle, but the change in the charge amount due to long-term use due to the presence of the excess coupling agent. Is caused.

Further, in the case of coating with a resin, the amount used is preferably 0.005 to 4.0% by mass in order to increase the adhesion strength of the resin.

The particle size of the magnetic carrier powder according to the present invention coated with a coupling agent has an average particle diameter of 1
0 to 200 μm is preferred. When the average particle diameter is less than 10 μm, the magnetic carrier particles themselves fly to the photoreceptor, causing a so-called carrier adhesion that causes a defect on an image. If it exceeds 200 μm, it will be difficult to obtain a clear image.

In particular, for high image quality and high quality, the average particle diameter is more preferably in the range of 10 to 50 μm, and more preferably, the average particle diameter is 15 to 45 μm. Even when a large number of original continuous prints are performed, it is more preferable in that the mixed toner transportability of the replenishment toner is excellent.

The magnetic carrier according to the present invention may be
A resin may be further coated on the coating of the coupling agent.

The resin to be coated may be any known resin, for example, epoxy resin, silicone resin,
Polyester resin, fluorine resin, styrene resin, acrylic resin, phenol resin and the like can be used. A polymer obtained by polymerizing from a monomer may be used. Considering the matching with the yellow toner of the present invention, a silicone resin is preferred.

Examples of the silicone resin include condensation reaction type silicone resins in which the substituent is a methyl group. Commercially available resins include SR2410 and SR241.
1 (manufactured by Dow Corning Silicone Toray), KR25
5 and KR251 (manufactured by Shin-Etsu Silicone Co., Ltd.). Resin-modified silicone can also be used. For example, epoxy-modified silicone resin such as SR21
15 and SR2145 (manufactured by Dow Corning Toray Silicone Co., Ltd.), ES1001N and ES1002T (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.

More preferably, the binder resin of the core particles is contained in a phenolic resin, the surface treating agent of the magnetic fine particles is contained in an epoxy group-containing silane coupling agent or a silicone coat resin, or an amino group is contained as a pretreatment agent for the core agent. By making the silane coupling agent to be, the silane coupling agent containing an amino group is hydrolyzed by moisture appropriately adsorbed in the binder resin, while forming a hydrogen bond with the hydroxyl group of the phenol resin, At the same time as self-condensing or condensing with the remaining silanol groups in the silicone resin to form a strong coating, the amino groups react with the epoxy group of the surface treatment agent of the magnetic fine particles, improving the adhesion of the silicone resin, The loss of the coating resin and the like are suppressed.

The amount of the resin to be coated is 0.1 to the composite particles.
It is preferably at least 05% by mass, and if it is less than 0.05% by mass, an insufficient and non-uniform film tends to be formed, making it difficult to freely control the charge amount. On the other hand, if the coating amount is too large, the electrical resistance of the composite particles becomes too high, causing a problem on the image. The content is more preferably 0.1 to 10% by mass, and even more preferably 0.2 to 5% by mass to prevent coalescence of particles during resin coating.

In the resin coating, a coupling agent may be contained, if necessary, in an amount of 0.1 to 20.0% by mass based on the solid content of the resin. As the coupling agent, a silane coupling agent is preferable. More preferably, 0.1 to 1 to prevent a reduction in strength due to self-condensation of the coupling agent.
0.0% by mass.

The magnetic resin carrier of the present invention has a true specific gravity of 2.5 to 4.5 (preferably 3.0 to 4.3). When the true specific gravity is within this range, the magnetic resin carrier and the toner The load on the toner during stirring and mixing with
It is preferable because contamination of the carrier surface by the toner is suppressed, and carrier adhesion to a non-image portion on the electrostatic image carrier is suppressed.

The magnetic resin carrier of the present invention has a size of 1000 ×
(10^Three/ 4π) · A / m (1000 Oersteds)
Magnetization strength measured under a magnetic field (σ₁₀₀₀) Is 15 to 60
Am _Two/ Kg (emu / g) (preferably 20 to 5
5 Am^Two/ Kg) and the residual magnetization (σ_r) Is 0.1 to 2
0 Am^Two/ Kg (emu / g) (preferably 0.3
10 Am^Two/ Kg) and the magnetic properties of the magnetic resin carrier
If the characteristics are within this range, the developer carrier (the developing three
Magnetic field generating means (for example, fixed magnetic
Under the magnetic field of the stone)
Carrier adhesion to the carrier is prevented, and the magnetic properties of the two-component developer
The compressive force on the toner in the air brush is reduced and external additives and
Preferred because carrier contamination by toner particles is suppressed
No. Residual magnetization of magnetic resin carrier (σ_r) Is 20 Am^Two/
If the weight exceeds 100 kg, the two-component developer on the developer carrier
Exchange with the two-component developer in the imager is not performed smoothly,
Variation in toner charge-up and toner charge
It is easy to occur.

Since the magnetic resin carrier of the present invention has a relatively high specific resistance value of 10 ^{11 to} 5 × 10 ¹⁵ Ω · cm, it is difficult for the carrier to adhere to the electrostatic image carrier, but the charge of the carrier itself is reduced. Since the number of leak sites is reduced, such as when continuously printing out originals with a high printing ratio,
The ability to impart charge to the toner is likely to be reduced. Nevertheless, the magnetic resin carrier of the present invention has a relatively low resistance magnetite dispersed therein and has a high resistance carrier, so that the carrier itself is less likely to be charged up than the conventional high resistance ferrite, but its latitude is narrow. Things. However, in the present invention, the oxycarboxylic acid present on the surface of the toner is contained in a specific amount, thereby preventing charge-up of the carrier and stabilizing the charge of the toner. Although the reason is not clear, the oxycarboxylic acid present on the toner surface is relatively easy to adsorb moisture, and due to its manufacturing method, it exists in a thin layer on the toner surface. It is presumed that it effectively acts to prevent charge-up and stabilizes the charge of the toner for a long period of time.

In order to make the resistance value and magnetic characteristics of the carrier fall within predetermined ranges, it is preferable that a non-magnetic inorganic compound is added to the carrier core in addition to the magnetic fine particles. The total amount of the magnetic fine particles and the nonmagnetic inorganic compound fine particles is 70 to 99% by mass (based on a carrier) (more preferably,
(80 to 99% by mass) is preferable in terms of the adjustment of the true specific gravity of the carrier, the adjustment of the specific resistance value of the carrier, and the mechanical strength of the carrier core.

Further, the specific resistance of the nonmagnetic inorganic compound fine particles is larger than that of the magnetic fine particles, and the larger the number average particle diameter of the nonmagnetic inorganic compound fine particles than that of the magnetic fine particles, the higher the specific resistance of the carrier. This is preferable for increasing the value and reducing the true specific gravity of the carrier.

The fact that the magnetic fine particles are contained in an amount of 30 to 95% by mass with respect to the total amount of the magnetic fine particles and the non-magnetic inorganic compound fine particles prevents the carrier from adhering by adjusting the magnetic force of the carrier. It is preferable for adjusting the specific resistance.

The shape of the magnetic resin carrier is appropriately selected so as to be suitable for a predetermined system. However, the sphericity of the magnetic resin carrier is 100 to 130.
(More preferably 100 to 120). When the magnetic resin carrier has a sphericity of more than 130, the fluidity as a developer becomes inferior, and the frictional charging ability to the toner is lowered, and the shape of the magnetic brush becomes uneven at the developing pole. It becomes difficult to obtain a high-quality image.

The sphericity of the carrier was measured using a field emission scanning electron microscope S-Hitachi, Ltd.
This is performed by extracting 300 or more carriers at random using 800, and using a Luzex3 image processing / analysis device manufactured by Nireco to determine the sphericity derived by the following equation.

[0182]

(Equation 5) [Where MXLNG indicates the maximum diameter of the carrier, and ARE
A indicates the projected area of the carrier. ]

Here, SF-1 closer to 100 means closer to a sphere.

Next, a method for producing a magnetic carrier according to the present invention will be described.

The treatment of the inorganic compound particle powder with the lipophilic treatment agent may be carried out by adding and mixing a solution of a coupling agent or an organic compound to the inorganic compound particle powder.

The composite particles are obtained by dispersing an inorganic compound particle powder dispersed in a solvent into a monomer constituting a binder resin, adding an initiator or a catalyst, and polymerizing the mixture.
It can be produced by a polymerization method or a so-called kneading and pulverizing method in which a binder resin containing inorganic compound particle powder is pulverized. A polymerization method is preferred for easily controlling the particle size of the magnetic carrier and obtaining a sharp particle size distribution.

In the production of composite particles using a phenol resin as a binder resin, for example, phenols and aldehydes and an inorganic compound particle powder which has been subjected to lipophilic treatment are dispersed in an aqueous medium, and a basic catalyst is added. Reaction. A method of forming a so-called modified phenol resin by mixing and reacting a natural resin such as rosin or a drying oil such as tung oil or linseed oil with phenols is also included.

In the case where the binder resin is a phenol resin, it is preferable because it retains a suitable amount of adsorbed water, promotes the hydrolysis of the coupling agent, and forms a strong coating.

In the production of composite particles using an epoxy resin as a binder resin, for example, bisphenols, epihalohydrin and lipophilic inorganic compound particles are dispersed in an aqueous medium, and the reaction is performed in an alkaline aqueous medium. There is a method to make it.

In the production of composite particles using a melamine resin as a binder resin, for example, a melamine and an aldehyde and an oleophilic inorganic compound particle powder are dispersed in an aqueous medium, and a weak acidic catalyst is dispersed. Reaction in the presence of

Other methods for producing composite particles using a thermosetting resin include, for example, kneading inorganic compound particle powder which has been subjected to lipophilic treatment with various resins, followed by pulverization.
Further, a method of performing a spheroidizing process and the like can be mentioned.

The composite particles composed of the inorganic compound particles and the binder resin which have been subjected to the lipophilic treatment may be subjected to a heat treatment if necessary in order to further harden the resin. It is particularly preferable to carry out the reaction under reduced pressure or in an inert atmosphere in order to prevent oxidation of the inorganic compound fine particles and the like.

The coating treatment of the composite particles with the coupling agent may be carried out by immersing the composite particles in water or a solvent in which the coupling agent is dissolved by a conventional method, followed by filtration and drying. A method of spraying and drying an aqueous solution or a solvent solution of the coupling agent with stirring is used. In particular, in order to prevent coalescence of the composite particles and form a uniform coating layer, a method of performing treatment with stirring is preferable.

The coating of the resin may be performed by a known method, for example, a method of dry-mixing the composite particles and the resin using a Henschel mixer or a high-speed mixer, or a method of coating the composite particles in a solvent containing the resin. How to impregnate,
Any method such as spraying a resin onto the composite particles using a spray dryer may be used.

Further, a method of reacting the composite particles with phenols, aldehydes, or melamines and aldehydes in an aqueous medium to coat a phenol resin or a melamine resin, or a mixture of acrylonitrile and another vinyl monomer May be polymerized in an aqueous medium to coat an acrylonitrile-based polymer, or a method of coating a polyamide resin by anionic polymerization of lactams.

Here, a method for measuring the characteristic value used for the magnetic carrier of the present invention will be described.

(Measurement Method of Carrier Characteristic Value) The average particle diameter is shown by a value measured by a laser diffraction type particle size distribution meter (manufactured by Horiba, Ltd.). Hitachi, Ltd., S-8
00).

The magnetization value (σ ₁₀₀₀ ) and the remanence magnetization value were measured using a vibrating sample magnetometer VSM-3S-15 (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 1 kOe.

The true specific gravity was indicated by a value measured with a multi-volume densitometer (manufactured by Micromeritics).

The volume resistivity was indicated by a value measured with a high resistance meter 4329A (produced by Yokogawa Hewlett-Packard).

Preferred embodiments of the magnetic resin carrier core of the present invention will be described.

In the reaction, first, magnetic fine particles and non-magnetic inorganic compound fine particles treated with a phenol, a formalin, water, and a coupling agent having an epoxy group are charged into a reaction vessel, and sufficiently stirred. A catalyst is added and the temperature is raised while stirring, the reaction temperature is adjusted to 70 to 90 ° C., and the phenol resin is cured. At this time, it is preferable to slowly raise the temperature in order to obtain spherical composite particles having a high sphericity. The heating rate is preferably 0.5 to 1.5 ° C./min,
More preferably, it is 0.8 to 1.2 ° C./min.

After the cured reaction product is cooled to 40 ° C. or lower, the obtained aqueous dispersion is separated into solid and liquid by a conventional method such as filtration and centrifugation, and then washed and dried to remove magnetic fine particles. Spherical carrier core particles obtained by combining nonmagnetic inorganic compound fine particles with a phenol resin as a binder resin are obtained. The production of the carrier core particles may be a batch type or a continuous type.

Further, as a method of coating the surface of the carrier core with a resin, there is a method of applying a coating solution prepared by dissolving or suspending the resin in a solvent to the surface of the carrier core.

In the present invention, when a two-component developer is prepared by mixing a toner and a carrier, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results can be obtained. If the toner concentration is less than 2% by mass, the image density tends to be low, and if it exceeds 15% by mass, fogging and scattering in the machine easily occur, and the useful life of the developer tends to decrease.

[0206]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

Toner Production Example 1 360 parts by mass of ion-exchanged water and 430 parts by mass of a 0.1 mol / l Na ₃ PO ₄ aqueous solution were added to a four-necked container.
15,000 rpm using a high-speed stirrer CLEAR MIXER
While stirring at m, the temperature was maintained at 60 ° C. After adding 10 parts by mass of 1N hydrochloric acid, 1.0 mol / l-
34 parts by mass of a CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . At this time, the pH in the aqueous medium was 5.3.

On the other hand, dispersoids include: styrene monomer 83 parts by mass n-butyl acrylate 17 parts by mass I. Pigment Yellow 93 3 parts by mass C.I. I. Solvent Yellow 162 3 parts by weight ・ Polyester resin 5 parts by weight (Mw = 1200, Mn = 5700, acid value 10 mgKOH / g) ・ Divinylbenzene 0.2 parts by weight ・ The oxycarboxylic acid (1-A) 0.05 parts by weight A mixture consisting of 12.5 parts by mass of ester wax (melting point = 60 ° C.) was dispersed for 4 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), and then 2,2′-azobis (2,4-dimethylvaleronitrile) 3 parts by mass were added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer was added to the aqueous dispersion medium.
The body composition is charged and N at an internal temperature of 70 ° C. _TwoAtmosphere, high speed
While maintaining the rotation speed of the stirrer at 15000 rpm, 4
After stirring for minutes, the polymerizable monomer composition was granulated. That
Then, the stirring device was replaced with a paddle stirring blade,
Hold at the same temperature while stirring at 00 rpm and polymerize for 5 hours
Was done. Then, the temperature was raised to 80 ° C, and sodium carbonate was removed.
And adjust the pH in the aqueous medium to 10 for another 5 hours.
Was performed. After the polymerization is completed, the remaining monomer is
After cooling, dilute hydrochloric acid was added after cooling, and the aqueous dispersion medium was added.
Adjust the body pH to 1.2 and dissolve the poorly water-soluble dispersant
Was. Furthermore, after solid-liquid separation by pressure filtration, 20,000 mass
Washing was performed with a portion of water. Then, a fluidized bed dryer (Okawa
4 hours at 45 ° C using Hara Seisakusho)
Yellow toner particles having a diameter of 6.4 μm were obtained.

100 parts by mass of the above polymer particles and 0.7 of hydrophobic oil-treated silica fine powder (BET: 200 m ^{2 /} g)
The parts by mass were dry-mixed with a Henschel mixer (manufactured by Mitsui Kinzoku Co., Ltd.) to obtain a toner (toner (A)).

Toner Production Example 2 In toner production example 1, the amount of oxycarboxylic acid added was 0.13 parts by mass, and C.I. I. Pigment Yellow
ow 93, 2 parts by mass, C.I. I. Solven
The toner was produced in the same manner as in Production Example 1 of the toner except that the amount of t Yellow 162 was changed to 1 part by mass. The obtained toner was designated as a toner (B).

Toner Production Example 3 In toner production example 1, the amount of oxycarboxylic acid added was 0.005 parts by mass, and C.I. I. Pigment Yel
low 93 was added in an amount of 5 parts by mass, and C.I. I. Solve
The toner was manufactured in the same manner as in Production Example 1 of the toner except that the amount of nt Yellow 162 was changed to 10 parts by mass. The obtained toner was designated as a toner (C).

Toner Production Example 4 In toner production example 1, C.I. I. Pigment
The addition amount of Yellow 93 was 10 parts by mass, and C.I. I. S
The toner was produced in the same manner as in Production Example 1 of the toner except that the amount of solvent Yellow 162 was changed to 2 parts by mass. The obtained toner was designated as a toner (D).

Toner Production Example 5 In toner production example 1, C.I. I. Pigment
The addition amount of Yellow 93 was 2 parts by mass, and C.I. I. So
The toner was manufactured in the same manner as in Production Example 1 of the toner, except that the amount of Lvent Yellow 162 was changed to 10 parts by mass. The obtained toner was designated as a toner (E).

Toner Production Example 6 A toner was produced in the same manner as in Toner Production Example 1, except that the amount of the initiator was changed to 10 parts by mass. The obtained toner was designated as toner (F).

Toner Production Example 7 A toner was produced in the same manner as in Toner Production Example 1, except that the amount of the initiator was changed to 0.1 part by mass. The obtained toner was defined as a toner (G).

Toner Production Example 8 Toner (A) was subjected to spheroidizing treatment in a hot water bath. The obtained toner was designated as toner (H).

Toner Production Example 9 100 parts by mass of styrene-butyl acrylate copolymer resin (styrene / butyl acrylate = 83/17) I. Pigment Yellow 93 3 parts by mass C.I. I. Solvent Yellow 162 3 parts by weight ・ Polyester resin 5 parts by weight (Mw = 1200, Mn = 5700, acid value 10 mgKOH / g) ・ Oxycarboxylic acid (1-A) 0.1 part by weight ・ Ester wax (melting point = 60 ° C.) ) The mixture consisting of 5 parts by mass was pulverized after melt-kneading. Then, FIG.
The classification was carried out using a classifier utilizing the crossed airflow and Coanda effect as shown in FIG. The obtained toner was designated as a toner (I).

Toner Production Example 10 A toner was produced in the same manner as in Toner Production Example 9 except that the classification conditions were changed. The obtained toner was designated as a toner (J).

Toner Production Example 11 A toner was produced in the same manner as in Toner Production Example 9 except that the classification conditions were changed. The obtained toner was designated as toner (K).

Toner Production Example 12 In toner production example 1, C.I. I. Pigment
Yellow 93 was added in an amount of 1 part by mass, C.I. I. So
The toner was manufactured in the same manner as in Production Example 1 of the toner except that the amount of Lvent Yellow 162 was changed to 1 part by mass and the amount of oxycarboxylic acid was changed to 0.14 part by mass. The obtained toner was designated as a toner (a).

Toner Production Example 13 In toner production example 1, C.I. I. Pigment
The addition amount of Yellow 93 was 10 parts by mass, and C.I. I. S
The toner was manufactured in the same manner as in Production Example 1 of the toner except that the amount of the solvent added to Yellow Yellow 162 was changed to 10 parts by mass and the amount of the oxycarboxylic acid was changed to 0.005 parts by mass. The obtained toner was designated as a toner (b).

Toner Production Example 14 In the toner production example 1, no sodium carbonate was added at the stage of raising the temperature to 80 ° C. in the latter half of the polymerization, and p
The toner was produced in the same manner as in Production Example 1 of the toner except that H was polymerized at 5.3. The obtained toner was designated as toner (c).

Toner Production Example 15 A toner was produced in the same manner as in Toner Production Example 1, except that the amount of oxycarboxylic acid was changed to 5.5 parts by mass. The obtained toner was designated as a toner (d).

Table 2 shows the physical property values of the above toner.

[0226]

[Table 2]

Production Example 1 of Developing Carrier 1 Phenol (hydroxybenzene) 50 parts by mass Formalin aqueous solution (formaldehyde about 40%, methanol about 10%, remainder water) 80 parts by weight Water 140 parts by weight Epoxy group Silane-based coupling agent KBM403 containing alumina surface-treated with Shin-Etsu Chemical Co., Ltd. 280 parts by mass of magnetite fine particles (number average particle size 0.24 μm, specific resistance value 5 × 10 ⁵ Ω · cm) KBM403 Α-Fe ₂ O ₃ fine particles surface-treated with 120 parts by mass (number-average particle size 0.40 μm, specific resistance value 8 × 10 ⁹ Ω · cm) ・ 25 wt% ammonia water 15 parts by mass

The above-mentioned materials were put in a four-necked flask, and the temperature was raised to 85 ° C. for 60 minutes while stirring and mixing, and the mixture was reacted and cured for 120 minutes. After cooling to 30 ° C. and addition of 500 parts by weight of water, the supernatant was removed, and the precipitate was washed with water and air-dried. Then, this is put under reduced pressure (5 mmHg) 1
After drying at 50 to 180 ° C. for 24 hours, a carrier core using a phenol resin as a binder resin was obtained.

On the surface of the obtained carrier core, γ-aminopropyltrimethoxysilane

[0230]

Embedded image Of a 5% by mass toluene solution was applied.

The surface of the carrier core has a γ of 0.2% by mass.
-Has been treated with aminopropyltrimethoxysilane. During the application, the toluene was volatilized while applying while continuously applying shear stress to the carrier core. On the surface of the carrier core

[0232]

Embedded image Was confirmed to be present.

While stirring the carrier core treated with the silane coupling agent by the above method at 70 ° C., the silicone resin KR-221 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added with 3% of the solid content of the silicone resin. After adding γ-aminopropyltrimethoxysilane and diluting with toluene so as to have a silicone resin solid content of 20%, the mixture was added under reduced pressure to coat the resin.

Thereafter, after stirring for 2 hours, heat treatment was performed at 140 ° C. for 2 hours in an atmosphere of nitrogen gas to loosen agglomerates, and coarse particles of 200 mesh or more were removed to obtain a carrier (1).

Production Example 2 of Developing Carrier A carrier was produced in the same manner as in Production Example 1 of the developing carrier except that urea was used instead of phenol. The obtained carrier is referred to as carrier (2).

Production Example 3 of Developing Carrier A carrier was produced in the same manner as in Production Example 1 of the developing carrier except that Mg—Mn—Fe ferrite was added instead of magnetite and hematite that had been hydrophobized. The obtained carrier is referred to as a carrier (3).

Production Example 4 of Developing Carrier Production Example 3 of Developing Carrier, except that polyvinylidene fluoride was used as a coating agent used on the carrier surface.
It was manufactured in the same manner as described above. The obtained carrier is referred to as carrier (4).

Production Example 5 of Developing Carrier A carrier was produced in the same manner as in Production Example 3 of the developing carrier, except that the surface of the carrier was not coated. The obtained carrier is referred to as a carrier (5).

Production Example 6 of Developing Carrier The production was carried out in the same manner as in Production Example 1 of the developing carrier, except that the polymerization conditions were changed. The obtained carrier is referred to as carrier (6).

Production Example 7 of Developing Carrier The production was carried out in the same manner as in Production Example 1 of the developing carrier, except that the polymerization conditions were changed. The obtained carrier is referred to as a carrier (7).

Production Example 8 of Developing Carrier The production was carried out in the same manner as in Production Example 1 of the developing carrier, except that the polymerization conditions were changed. The obtained carrier is referred to as a carrier (8).

Table 3 shows the weight-average diameter, SF-1 and volume resistance of the carrier obtained by the above-mentioned method for producing a carrier for development.

[0243]

[Table 3]

Light resistance and OHP transparency were evaluated by the following methods. Further, for a developer having no problem in light fastness and OHP transparency (both light fastness and OHP transparency are above C level), the initial printout image evaluation of 5,000 sheets and 10,000 sheets was performed by the following method, and the image was evaluated. The density, fog transferability and fixability were measured. Table 4 shows the evaluation results.

The preparation of the two-component developer was carried out using the carrier 92.
Parts by mass and 8 parts by mass of the yellow toner were mixed by a V-type mixer so that the toner concentration became 8%.

The obtained two-component developer is placed in the developing units R1 and R2, which are the unit shown in FIG. 2, and mounted in the image forming apparatus shown in FIG. 3, and the initial solid image density is 1 in the mono color mode. The printout image evaluation was performed on an image of A4 size and a printing rate of 6%.

<Method for Evaluating Lightfastness> A Macbeth reflection densitometer RD9 was used on plain paper (75 g / m ² ) for ordinary copying machines.
18c (manufactured by Macbeth Co., Ltd.) and the image density becomes 1.5.
After irradiating a solid image of mx 5 cm with a carbon arc lamp for 100 hours and measuring the image density in the same manner as above, A: 1.40 or more B: 1.30 or more and less than 1.40 C: 1.20 or more 1 Less than .30 D: Less than 1.20

<Method for Evaluating OHP Transparency> Obtained OH
The transmittance and the haze (haze) for each toner amount per unit area of the T-fixed image were measured, and the transparency was evaluated using a numerical value at an image density of 1.5. The method for measuring the transmittance and haze is described below.

The transmittance was measured using a Shimadzu self-recording spectrophotometer UV.
Using 2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone is set to 100%, and the transmittance at the maximum absorption wavelength at 650 nm is measured.

The haze was measured using a haze meter ND.
The measurement was performed using H-300A (manufactured by Nippon Shikara Kogyo Co., Ltd.). A: 90% or more B: 80% or more and less than 90% C: 70% or more and less than 80% D: less than 70%

<Method of Measuring Image Density> Evaluation was performed based on the image density when a predetermined number of printouts were completed on ordinary plain paper for copying machines (75 g / m ² ). The image density was measured using a Macbeth reflection densitometer (manufactured by Macbeth) to measure the relative density of a white background portion having a document density of 0.00 with respect to the printout image.

<Method of Measuring Fog> The measurement of fog was performed using a REFLECTOMETER MODEL manufactured by Tokyo Denshoku Co., Ltd.
The measurement was performed using TC-6DS, and the yellow toner image was calculated by the following equation using a Blue filter. The smaller the value, the less fog.

Fog (reflectance) (%) = [Reflectance of standard paper (%)] − [Reflectance of non-image portion of sample (%)]

<Evaluation Method of Transferability> After printing out 10,000 sheets, the “surprise” character pattern shown in FIG. 6A was printed out on a cardboard (128 g / m ² ), and the character part was missing. (The state of FIG. 6B) was visually evaluated. A: Almost no occurrence B: Slight hollowing out C: Slight hollowing out D: Slightly hollowing out E: Extremely hollowing out

<Method of Evaluating Fixability> An unfixed solid image (toner development amount is 0.1%) at the beginning of printout evaluation.
(Prepared to be 7 mg to 0.8 mg) was fixed by an offline fixing device (fixing device shown in FIG. 4). Thereafter, the state of adhesion of the toner to the fixing roller was visually evaluated. A: Not generated. B: Slight sticking is observed. C: There are sticking and scratches. D: Many sticks.

[Example 1] Evaluation was made using carrier (1) as a carrier and toner (A) as a toner.
As a result, good results were obtained for each item.

Example 2 Example 1 was the same as Example 1 except that the toner (A) was replaced with the toner (B).
The evaluation was performed in the same manner as described above. As a result, the lightfastness level was slightly reduced. This is presumed to be due to the small value of A / B. However, it was at a level without problems.

Example 3 Example 1 was repeated except that toner (A) was replaced with toner (C).
The evaluation was performed in the same manner as described above. As a result, the level of fog decreased slightly. This is presumed to be because the value of A / B is slightly too large.

Example 4 Example 1 was the same as Example 1 except that toner (A) was replaced with toner (D).
The evaluation was performed in the same manner as described above. As a result, the image was slightly inferior in yellow color visually. However, good results were obtained in other items.

Example 5 Example 1 was the same as Example 1 except that the toner (A) was replaced with the toner (E).
The evaluation was performed in the same manner as described above. As a result, the image was slightly inferior in yellow color visually. However, good results were obtained in other items.

Example 6 Example 1 was repeated except that toner (A) was replaced with toner (F).
The evaluation was performed in the same manner as described above. As a result, the fixability was slightly inferior. This is presumed to be due to the small weight average molecular weight.

Example 7 Example 1 was the same as Example 1 except that the toner (A) was replaced with the toner (G).
The evaluation was performed in the same manner as described above. As a result, the fixing property and the OHP transparency were slightly inferior. This is presumed to be because the weight average molecular weight was too large.

Example 8 Example 1 was repeated except that toner (A) was replaced with toner (H).
The evaluation was performed in the same manner as described above. As a result, the fog worsened. This is presumably because the average circularity of the toner was too large and the external additives were released.

Example 9 Example 1 was the same as Example 1 except that the toner (A) was replaced with the toner (I).
The evaluation was performed in the same manner as described above. As a result, slight deterioration of transferability was observed. This is presumed to be because the average circularity of the toner is too small.

Example 10 Example 10 was the same as Example 1 except that the toner (A) was replaced with the toner (J).
The evaluation was performed in the same manner as described above. As a result, the transferability was slightly deteriorated. This is presumed to be because the average circularity of the toner is too small.

Example 11 Example 1 was repeated except that toner (A) was replaced with toner (K).
The evaluation was performed in the same manner as described above. As a result, transferability was deteriorated. This is presumed to be because the average circularity of the toner is too small. However, it was at a level without problems.

Comparative Example 1 Example 1 was repeated except that toner (A) was replaced with toner (a).
The evaluation was performed in the same manner as described above. As a result, the light resistance was significantly deteriorated, so that the printout image evaluation was not performed. It is assumed that the remarkable decrease in light fastness is due to the value of A / B being too small.

Comparative Example 2 Example 1 was repeated except that toner (A) was replaced with toner (b).
The evaluation was performed in the same manner as described above. As a result, a remarkable decrease in image density occurred at the end of 5,000 sheets, and the evaluation was stopped. This is presumed to be because the value of A / B was too large and charge-up of the developer occurred during printout.

Comparative Example 3 Example 1 was repeated except that toner (A) was replaced with toner (c).
The evaluation was performed in the same manner as described above. As a result, remarkable fog occurred from the beginning, and the evaluation was stopped. This is presumed to be because the value of B is too small.

Comparative Example 4 Example 1 was repeated except that toner (A) was replaced with toner (d).
The evaluation was performed in the same manner as described above. As a result, remarkable fog occurred from the beginning, and the evaluation was stopped. This is presumed to be because the value of B is too large.

Example 12 An image was formed in the same manner as in Example 1 except that the carrier (2) was used. As a result, fog slightly deteriorated. This is presumably because the hardness of the urea resin was slightly inferior and toner spent was likely to occur.

Example 13 An image was formed in the same manner as in Example 1 except that the carrier (3) was used. As a result, fog slightly deteriorated. This is Mg-
This is probably because Mn-Fe particles were used.

Example 14 An image was formed in the same manner as in Example 1 except that the carrier (4) was used. As a result, fog slightly deteriorated. This is presumably because the coating material was polyvinylidene fluoride, which reduced the charge amount.

Example 15 An image was formed in the same manner as in Example 1 except that the carrier (5) was used. As a result, fog slightly deteriorated. This is probably because the carrier amount was not covered with the coating material, and the charge amount of the developer was reduced.

Example 16 An image was formed in the same manner as in Example 1 except that the carrier (6) was used. As a result, fog slightly deteriorated. This is probably because the value of SF-1 of the carrier is slightly too large.

Example 17 An image was formed in the same manner as in Example 1 except that the carrier (7) was used. As a result, fog slightly deteriorated. This is considered to be due to the high resistance of the carrier.

Example 18 An image was formed in the same manner as in Example 1 except that the carrier (8) was used. As a result, fog slightly deteriorated. This is considered to be because the resistance of the carrier is small.

Light resistance at the beginning of Examples and Comparative Examples,
Table 4 shows the evaluation results of OHP transparency, image density, and fog.

[0279]

[Table 4]

[0280]

As described above, the yellow toner and the developer for the yellow toner of the present invention are excellent in image density, fog suppression, transparency, light resistance, transferability and fixability.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of an absorption spectrum of oxycarboxylic acid.

FIG. 2 is a schematic explanatory view illustrating an example of a developing device unit of the image forming apparatus.

FIG. 3 is a schematic explanatory view showing an example of an image forming apparatus to which the toner of the present invention can be applied.

FIG. 4 is a schematic explanatory view showing an example of a fixing device.

FIG. 5 is an explanatory diagram of an airflow classification device.

FIG. 6 is a schematic diagram showing a state of missing characters.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Photoreceptor 12 Charging roller 13 Image exposure 14 Developing device 15 Intermediate transfer member 16 Primary transfer bias 17 Cleaning roller 18 Fixing device 19 Cleaning means 20 Transfer belt 30 Stay 31 Heating body 31a Heater substrate 31b Heating body 31c Surface protection layer 31d Temperature sensing element 32 Fixing Film 33 Pressure Roller 34 Coil Spring 35 Film End Regulating Flange 36 Power Supply Connector 37 Disconnecting Member 38 Inlet Guide 39 Outlet Guide (Separation Guide) 41 Developing Sleeve 42 Magnet Roller 43, 44 Developer Conveying Screw 49 Developer 49a Toner 49b Carrier 51 Charging roller 52 Developing container 61a Photosensitive drum 62a Primary charging device 63a Developing device 64a Transfer blade 65a Replenishing toner 67a Laser light 68 Transfer material carrier 69 Separating charger 70 Fixing device 71 Fixing roller 72 Pressure roller 73 Web 75, 76 Heating means 79 Transfer belt cleaning device 80 Driving roller 81 Belt driven roller 82 Belt neutralizer 83 Registration roller 85 Toner density detection sensor 201 Airflow classifier 211 , 212,213 Outlet 214,215 Inlet pipe 216 Raw material supply nozzle 217,218 Classification edge 219 Inlet edge 220 First gas introduction control means 221 Second gas introduction control means 222,223 Side wall 224,225 Classification edge block 226 Coanda Block 227 Left block 228,229 Static pressure gauge 231 Injection nozzle 232 Classification chamber

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Taniuchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Naotaka Ikeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Kenichi Nakayama 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA01 AA06 AA15 AA21 BA03 BA06 CA04 CA12 CA21 CA26 CA30 DA01 EA01 EA06 EA07 EA10

Claims (21)

[Claims] 1. A yellow toner containing at least a binder resin, a yellow colorant, and an oxycarboxylic acid, wherein the yellow colorant is C.I. I. Pigment Yellow
ow 93, and / or C.I. I. Solvent Ye
and oxycarboxylic acid extracted from 0.1 g / g of yellow toner with 0.1 mol / l of sodium hydroxide aqueous solution. The mass of the acid is B (m
g), wherein A / B = 5 to 1000 B = 0.10 to 3.50. 2. The method according to claim 1, wherein the yellow colorant is at least C.I.
I. Pigment Yellow 93 and C.I. I. So
lvent Yellow 162, and the mass ratio of both contents is C.I. I. Pigmen
t Yellow 93: C.I. I. Solvent Y
2. The yellow toner according to claim 1, wherein the value of yellow 162 is from 25:75 to 75:25. 3. The yellow toner according to claim 1, wherein the oxycarboxylic acid is a compound represented by the following formula (1). Embedded image [In the above formula (1), (A) is selected from the following group, and X ₁
Represents a hydrogen atom, a sodium atom, a potassium atom, ammonium or an aliphatic ammonium. ] 4. The yellow toner according to claim 1, wherein the oxycarboxylic acid is a compound represented by the following formula (2). Embedded image [In the above formula (2), X ₂ represents a hydrogen atom, a sodium atom, a potassium atom, ammonium, or an aliphatic ammonium, and R ₄ represents a C _{1 to} C ₂₂ alkyl group or alkenyl group, or an aryl group. , R ₅ are hydrogen atoms, C ₁ -C
_{22 represents} an alkyl group, an alkenyl group, an aryl group, and an alkoxy group. ] 5. A flow-type circle equivalent diameter based on the number of toner measured by the particle image measuring device - in circularity scattergram, circle-equivalent number-average particle diameter D ₁ of the said toner 2~10μ
m, and the average circularity of the toner is 0.920 to
5. The yellow toner according to claim 1, wherein the circularity standard deviation is less than 0.040 at 0.995. 6. In a scattergram of a circle equivalent diameter-circularity based on the number of toners measured by a flow type particle image measuring apparatus, the average circularity is 0.950 to 0.995, and the circularity standard deviation is 0.5. The yellow toner according to any one of claims 1 to 5, wherein the yellow toner is less than 035. 7. In a scattergram of a circle equivalent diameter-circularity based on the number of toners measured by a flow type particle image measuring device, the average circularity is 0.975 to 0.995, and the circularity standard deviation is 0.1. The yellow toner according to any one of claims 1 to 5, wherein the yellow toner is not less than 015 and less than 0.035. 8. In a scattergram equivalent to a circle based on the number of toners measured by a flow-type particle image measuring apparatus, 15% by number of toner particles having a circularity of less than 0.950 are used.
The yellow toner according to claim 1, wherein: 9. The toner tetrahydrofuran (THF)
Has a weight-average molecular weight of 30,000 to 60 in gel permeation chromatography (GPC) of a soluble component of
The yellow toner according to any one of claims 1 to 8, wherein the yellow toner is 0000. 10. A two-component developer comprising at least a binder toner, a yellow colorant, and a yellow toner containing an oxycarboxylic acid and a carrier, wherein the yellow colorant is C.I. I. Pigment Yellow 93,
And / or C.I. I. Solvent Yellow 1
62 (each according to the name described in the color index 4th edition), the content of the yellow colorant is A (mg), and oxycarboxylic acid extracted from 1 g of the yellow toner with a 0.1 mol / liter aqueous sodium hydroxide solution Is the mass of B (m
g), A / B = 5 to 1000 B = 0.10 to 3.50, and the volume resistivity of the carrier is 10 ¹¹ to 10 ¹⁵ Ω · cm.
A yellow developer. 11. The method according to claim 11, wherein the yellow colorant is at least C.I.
I. Pigment Yellow 93 and C.I. I. So
lvent Yellow 162, and the mass ratio of both contents is C.I. I. Pigmen
t Yellow 93: C.I. I. Solvent Y
11. The yellow developer according to claim 10, wherein yellow 162 = 25: 75 to 75:25. 12. The yellow developer according to claim 10, wherein the oxycarboxylic acid is a compound represented by the following formula (1). Embedded image [In the above formula (1), (A) is selected from the following group, and X ₁
Represents a hydrogen atom, a sodium atom, a potassium atom, ammonium or an aliphatic ammonium. ] 13. The method according to claim 10, wherein the oxycarboxylic acid is a compound represented by the following formula (2).
3. The developer for yellow according to any one of 2. Embedded image [In the above formula (2), X ₂ represents a hydrogen atom, a sodium atom, a potassium atom, ammonium, or an aliphatic ammonium, and R ₄ represents a C _{1 to} C ₂₂ alkyl group or alkenyl group, or an aryl group. , R ₅ are hydrogen atoms, C ₁ -C
_{22 represents} an alkyl group, an alkenyl group, an aryl group, and an alkoxy group. ] 14. The flow type circle equivalent diameter based on the number of toner measured by the particle image measuring device - in circularity scattergram, circle-equivalent number-average particle diameter D ₁ of the said toner 2-10
μm, and the average circularity of the toner is 0.920.
The yellow developer according to any one of claims 10 to 13, wherein the circularity standard deviation is less than 0.040 and a circularity standard deviation is less than 0.040. 15. In a scattergram of circle equivalent diameter-circularity based on the number of toners measured by a flow type particle image measuring apparatus, the average circularity is 0.950 to 0.995, and the circularity standard deviation is 0.5. The yellow developer according to any one of claims 10 to 14, wherein the yellow developer is less than 035. 16. In a scattergram of a circle equivalent diameter-circularity based on the number of toners measured by a flow type particle image measuring device, the average circularity is 0.975 to 0.995, and the circularity standard deviation is 0.1. The yellow developer according to any one of claims 10 to 14, wherein the developer is 015 or more and less than 0.035. 17. In a scattergram corresponding to a circle based on the number of toners measured by a flow type particle image measuring apparatus, 15% by number of toner particles having a circularity of less than 0.950 are used.
17. The yellow developer according to claim 10, wherein: 18. The toner tetrahydrofuran (TH)
The soluble component of F) has a weight average molecular weight of 30,000 to 6 in gel permeation chromatography (GPC).
18. 00000.
The developer for yellow according to any one of the above. 19. The carrier is a magnetic fine particle-dispersed carrier formed of composite particles having at least inorganic compound particles and a binder resin, wherein the magnetic fine particle-dispersed carrier has an epoxy group on the surface of the composite particles, It has been treated with one or more coupling agents having one or more functional groups selected from an amino group and a mercapto group, and the inorganic compound particles have at least an epoxy group, a mercapto group, It is characterized by being treated with a lipophilic treatment agent having one or more functional groups selected from an organic acid group, a ketone group, a halogen group, a halogenated alkyl group and an aldehyde group, or a mixture thereof. The yellow developer according to claim 10. 20. The developer according to claim 19, wherein the binder resin forming the surface of the composite particles contains at least a phenol resin. 21. The yellow developer according to claim 19, wherein the surface of the composite particles is further coated with a resin.