JP2001343787A - Image forming toner and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for image formation and a device for image formation which have satisfactory rising property of electrification, environmental stability of electrification and offset resistance at high temperatures, offset resistance at low temperature, high productivity and superior storage property with respect to heat and with which images of high image quality can be obtained. SOLUTION: The toner for image formation is an electrostatic charge image developing toner and contains at least a binder resin, a coloring agent and a release agent. In the toner, at least a nonlinear polyester resin (A), containing a metal compound of aromatic oxycarboxylic acid having 30 to 70 mg KOH/g hydroxyl value and three or higher valences of the center metal, is used for the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming toner used in an image forming method such as an electrophotographic method or an electrostatic printing method, a two-component image forming developer, a container filled with the same, and a container equipped with the container. To an image forming apparatus.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and Japanese Patent Publication No. 49-23910 are used.
Various methods are described in Japanese Patent Publication No. JP-A-43-24748 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means.
Next, the latent image is developed using toner, and if necessary, a toner powder image is transferred to paper or the like, and then fixed by heating, pressing, or solvent vapor to obtain a copy image.

The methods of developing an electric latent image are roughly classified into a liquid developing method using a developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method,
There is a dry development method using a toner in which a coloring agent such as carbon black is dispersed in a natural or synthetic resin, such as a magnetic brush method and a powder cloud method. In recent years, the dry development method has been widely used.

As a fixing method in the electrophotographic method, a method in which a heating roller is directly pressed into contact with a toner image on a transfer material to fix the toner image from the viewpoint of downsizing, that is, a heat roller fixing method, is an energy efficiency. Widely used because of its goodness. It is desired to reduce the power consumption of the heat roller used for fixing from consideration for the environment of energy saving. As a method for solving this problem, the fixing device has been improved, and in order to further increase the thermal energy efficiency, the thermal energy efficiency is increased by reducing the thickness of the roller in contact with the toner image support surface. The time can be greatly reduced. However, since the specific heat capacity has become small, the temperature difference between the portion where the transfer material has passed and the portion where the transfer material has not passed has increased, and the molten toner has adhered to the fixing roller. Since the so-called hot offset phenomenon, which is fixed to the upper non-image area, occurs, the demand for toner for anti-hot offset is becoming more and more severe. Further, in recent years, thermal energy given to toner at the time of fixing, such as low-temperature fixing or high-speed copying for energy saving, tends to be small. It is generally attempted to improve the low-temperature fixability by using a resin or wax having a low softening point as the toner used for such low-temperature fixing.

In order to achieve both low-temperature fixability and high-temperature offset resistance, it has been studied to add a wax as a release agent to a toner component or to use a low-temperature fixable resin such as a polyester resin. Was. For example, JP-A-63-225244 and JP-A-63-2225
JP-A-25245 and JP-A-63-225246 disclose toners containing two kinds of linear polyesters, but they do not reach a level applicable from low speed to high speed. . Also, Japanese Patent Application Laid-Open No.
JP-A-8468 and JP-A-9-204071 disclose toners containing a resin in which the acid value, hydroxyl value, molecular weight distribution, THF-insoluble content and the like of the polyester resin are specified. Further improvement is necessary in all of the balances such as the anti-blocking property and the like.

As a method for solving such a problem,
A chelate compound having salicylic acid, oxysalicylic acid, or the like as a ligand is exemplified. A conventionally known metal complex salt of a salicylic acid derivative is disclosed in JP-A-62-1452.
No. 55 and Japanese Patent Publication No. 55-42752. However, it contains heavy metals such as Cr and Co, and has environmental problems.

Further, from the viewpoint of environmental considerations, studies on salicylic acid derivatives having Fe as a central metal containing no metal such as Cr have been known. Japanese Patent Application Laid-Open No. 1-309072 discloses an effect when limited to a metal complex of a salicylic acid derivative having a carboxyl group or a sulfoxyl group as a substituent. Also, JP-A-9-3
No. 25520 discloses an effect only in combination with a specific resin and in combination with an iron complex having salicylic acid as a ligand. JP-A-7-230188 and JP-A-10-10785 disclose the effect of a combination of a specific resin and an iron complex having oxycarboxylic acid as a ligand. However, these are effective only when limited to a specific structure of an iron salicylate complex or a specific resin and a salicylic acid complex, and are not limited to salicylic acid in which the substituent is not limited to a carboxyl group or a sulfoxyl group. The effects of the iron complex and the resin whose structure is not limited at all are not disclosed. Further, the charge control agent of the metal complex cannot predict the charging characteristics due to the difference in ligand, and the uniform dispersibility and charging characteristics of the resin.

In recent years, there has been an increasing demand for higher image quality of copy images, and a reduction in toner particle size has been required. However, reducing the particle size of the toner improves the image quality, but also causes various problems. In particular, in fixing,
The fixability of the halftone portion is deteriorated. This is because the toner transferred to the concave portion on the transfer material has an extremely small amount of heat applied from the fixing roller because the halftone portion has a small amount of adhered toner, and the offset phenomenon is likely to occur. .

[0009]

SUMMARY OF THE INVENTION Accordingly, the present invention has as its first object a charge rising property, a charging environmental stability,
Good high-temperature offset resistance, and as a second purpose,
An object of the present invention is to provide an image-forming toner and an image-forming apparatus that have good low-temperature offset properties, high productivity, excellent heat-resistant storage stability, and can obtain high-quality images.

[0010]

The object of the present invention is to provide (1) an electrostatic charge developing toner containing at least a binder resin, a colorant and a release agent. The hydroxyl value is 30 mgKOH / g to 70 mgKOH /
g. and at least a non-linear polyester resin (A) containing a metal compound of an aromatic oxycarboxylic acid having a trivalent or higher valence in the central metal ”, (2)“ the image forming toner ” A mixture containing a non-linear polyester resin (A), a linear polyester resin (B), a raw material monomer of a polycondensation resin, and a raw material monomer of an addition polymerization resin is used as a resin to be cured. (1) The image forming toner according to the above (1), which comprises a composite resin (C) of a polyester resin and a vinyl resin obtained by performing an addition polymerization reaction in parallel. 3) The image forming toner according to the above item (1) or (2), wherein the aromatic oxycarboxylic acid satisfies the following structural formula;

[0011]

Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
N, S, O, or a hetero atom of P may be included, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond,
R ₂ and R ₃ each independently represent an alkyl group, an alkenyl group,
Alkoxy group, aryl group or aryloxy group or aralkyl group or aralkyloxy group which may have a substituent, halogen group, hydrogen, hydroxyl group, amino group which may have a substituent, carboxyl group, carbonyl group, nitro group Group,
A nitroso group, a sulfonyl group, a cyano group, R ₄ represents a hydrogen or an alkyl group, l is an integer of 0 or 3 to 12, m is an integer of 1 to 20, n is an integer of 0 to 20,
o is an integer from 0 to 4, p is an integer from 0 to 4, q is an integer from 0 to 3, r is an integer from 1 to 20, and s is an integer from 0 to 20. M is a trivalent or higher metal. ]],
(4) “The image forming toner according to any one of the above items (1) to (3), wherein the central metal is Fe”, (5) “The central metal is Zr. (6) The image forming toner according to any one of the above items (1) to (3), wherein the releasing agent contains a free fatty acid-type carnauba wax. (7) The image forming toner according to any one of the above items (1) to (5), which is determined by a THF-soluble component of the toner (mainly a binder resin). Any one of the above items (1) to (6), wherein the value of the molecular weight distribution determined by GPC has at least a peak between 1,000 and 10,000, and the half width of the distribution is 15,000 or less. (1) Metal of monoazo dye as charge control agent Characterized in that said containing paragraph (1), second (7) toner image formation according to any one of claim ", (9)" toner volume average particle diameter D ₄ is 4~8μ
(1) to (8).
Item 10. An electrostatic charge developing toner according to any one of the above items), (10)
This is achieved by "the toner for electrostatic charge development according to any one of the above items (1) to (9), wherein the toner has an average circularity of 0.940 or more".

[0012] The object of the present invention is also characterized in that (11) the present invention is characterized by containing the image forming toner and the carrier according to any one of the above items (1) to (10). Component image forming developer ".

Still another object of the present invention is to provide (12) the present invention.
"An image forming toner container filled with the image forming toner according to any one of the above items (1) to (11)"; (14) An image forming developer container filled with the two-component image forming developer described above, (14) A container filled with the image forming toner described in (12) above is mounted. (15) The image forming apparatus characterized in that
(3) A developing container for image formation characterized by mounting a container filled with the developer for two-component image formation described in the item (3).

That is, the present inventors have conducted intensive studies and as a result, have found that the present invention relates to an electrostatic charge developing toner comprising at least a binder resin, a colorant and a release agent, wherein the hydroxyl value of the binder resin is 30 mg KOH. A first object of the present invention is to provide an image forming toner characterized in that the toner contains at least a non-linear polyester resin having a molecular weight of from 3 / g to 70 mgKOH / g and a metal compound having a trivalent or higher aromatic oxycarboxylic acid as a central metal. It has been found that a toner that can solve the above problem can be provided. This is because the hydroxyl value of the non-linear polyester resin forms a mild cross-linked structure with the aromatic oxycarboxylic acid metal complex.
Dimensionally connected, effective in hot offset properties,
In particular, when a thin fixing roller was used and a large-size transfer material was passed after a small-size transfer material, the effect of improving the occurrence of hot offset at the end was excellent. When the central metal of the aromatic oxycarboxylic acid compound was divalent, no improvement effect was observed. The content of the metal salicylate compound is 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. When the hydroxyl value of the polyester resin was less than 30 mgKOH / g, the effect of hot offset resistance was not sufficient. 70mgKOH
/ G, the hot offset resistance was sufficient, but the environmental stability of charging was low.

In particular, when the central metal is Fe,
The charge rising property was excellent.

In particular, when the central metal is Zr,
Since the compound is white, it can be used for color toners.

In particular, when a defatty acid-type carnauba wax is contained as the releasing agent, a toner having a more excellent releasing effect at the time of fixing, which has a further excellent hot offset property, can be obtained.

In the present invention, a mixture containing a linear polyester resin, a raw material monomer of a polycondensation resin, and a raw material monomer of an addition polymerization resin is used as the non-linear polyester resin.
When a polyester resin and a vinyl-based resin composite resin obtained by performing a condensation polymerization reaction and an addition polymerization reaction in parallel in the same reaction vessel are contained, the linear polyester resin has an effect on low-temperature offset properties and has a wide range. Thus, a toner excellent in productivity and heat-resistant storage stability can be obtained by finely dispersing the composite resin in two types of (A) and (B) polyester resins with excellent offset resistance.

Particularly, when the value of the molecular weight distribution by GPC determined by the THF-soluble component of the toner (mainly resin) is 1
It has been found that, by having at least one peak between 000 and 10,000 and having a half-value width of 15,000 or less in the distribution, the low-temperature offset property, which is far superior to the conventional one, is effective. GP used in the present invention
C (Gel Permeation Chromatography) is measured as follows. Stabilize the column in a heat chamber at 40 ° C., and add TH as a solvent to the column at this temperature.
F at a flow rate of 1 ml / min.
０．６0.6% by weight of a resin THF sample solution
Measure by injecting ~ 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure
Chemical Co. Alternatively, the molecular weight of Toyo Soda Kogyo KK is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ ,
1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ ,
3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48
It is appropriate to use × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In particular, the toner has a volume average particle diameter of 4 to 8 μm.
In the case of m, it was possible to obtain a high-quality image excellent in fine line reproducibility. When the thickness is less than 4 μm, fine line reproducibility is excellent, but cleaning performance is lacking, and a problem occurs in durability.

The volume average particle diameter of the toner can be measured by various methods.
An interface for outputting a volume distribution (manufactured by Nikkaki) and a PC9801 personal computer (manufactured by NEC) were used. The electrolytic solution was adjusted to a 1% NaCl aqueous solution using primary sodium chloride. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, is used as a dispersant in 50 to 100 ml of the electrolytic solution.
Add 1-5 ml and add 1-10 mg of sample. this,
Perform a dispersion treatment for 1 minute with an ultrasonic disperser, put 100 to 200 ml of the aqueous electrolytic solution in another beaker, add the sample dispersion liquid therein to a predetermined concentration, and use the Coulter Counter TA-II type. Using a 100 μm aperture as the aperture, measure the 30,000 particle size distribution of 2 to 40 μm particles based on the number, calculate the volume distribution and number distribution of the 2 to 40 μm particles, and calculate the weight-based volume obtained from the volume distribution. The average particle size (D ₄ : the median value of each channel is a representative value of the channel) was determined.

Particularly, the average circularity of the toner is 0.940.
In the cases described above, a good image with few transfer omissions in the line image was obtained. This is presumably because the toner surface is sufficiently smooth, so that the number of contact points with the image support decreases, and that the transfer of defective toner from the electrostatic charge holding member to the transfer material is reduced.

Here, the average circularity of the toner is measured by
Sysmex Flow Particle Image Analyzer FPIA-10
00 was used. The outline of the apparatus and measurement is described in JP-A-8-13.
No. 6439. After the measurement was adjusted to 1% NaCl aqueous solution using primary sodium chloride,
50-100 ml of liquid passed through a 0.45 μm filter
0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersing agent to the sample.
Add 0 mg. This was subjected to a dispersion treatment for 1 minute by an ultrasonic disperser, and the particle concentration was adjusted to 5,000 to 15,000 particles / μl.
The measurement was carried out using the dispersion adjusted as described above. The diameter of a circle having the same area as the two-dimensional image area captured by the CCD camera is defined as the equivalent circle diameter, and the equivalent circle diameter of 0.6 μm or more is effective from the accuracy of the CCD pixel and used for calculating the average circularity. Was. The average circularity can be obtained by calculating the circularity of each particle, adding the circularity of each particle, and dividing by the total number of particles. The average circularity of each particle can be calculated by dividing the perimeter of a circle having the same projected area as the particle image by the perimeter of the projected particle image. However, when the circularity is 0.4 or less, the circularity is set to 0.4. The smaller the value of the circularity, the more complicated the particle image and the more irregular the toner shape.

The method for producing the toner of the present invention is not limited.
An ordinary pulverization method, a production method other than the pulverization method such as a polymerization method, or a combination thereof may be used.

Next, the materials used for the toner of the present invention will be described in detail. The polyester resin used in the present invention is a polymer obtained by polycondensation of a polyhydroxy compound and a polybasic acid. Examples of the polyhydroxy compound include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; alicyclic compounds containing two hydroxyl groups such as 1.4-bis (hydroxymethyl) cyclohexane; and bisphenol A And the like. In addition, the polyhydroxy compound includes a compound containing three or more hydroxyl groups.

Examples of the polybasic acid include dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid;
Benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-
Examples thereof include trivalent or higher polyvalent carboxylic acid monomers such as octanetetracarboxylic acid. Here, the glass transition temperature Tg of the polyester resin is 55 ° C. from the relation of heat preservation.
More preferably, the temperature is more preferably 60 ° C. or higher.

In the polycondensation reaction between these polyhydric hydroxy compounds and polybasic acids, there are differences in the reaction raw materials and the like.
The obtained polyester resin may be a polymer having a non-linear structure or a polymer having a linear structure. In the present invention, it is considered that the non-linear polyester resin (A) exerts an effect on the hot offset property, and the linear polyester resin (B) exerts an effect on the low-temperature offset property. The non-linear polyester resin referred to in the present invention means a polyester resin having a substantial crosslinked structure, and the linear polyester resin means a polyester resin having substantially no crosslinked structure.

Although the hydroxyl value is limited in the present invention, a polyester resin having a desired hydroxyl value having a desired value can be obtained by the conditions of the esterification reaction. For the measurement of the hydroxyl value, a method specified in JIS K0070 was used.
However, if the sample does not dissolve, use a solvent such as dioxane or tetrahydrofuran as the solvent.

The molecular weight distribution of the toner has a great influence because the resin is most contained as a constituent material. As for the molecular weight distribution of the resin, a resin having a desired molecular weight distribution can be obtained by changing the degree of polymerization mainly by selecting a monomer material and a synthesis time at the time of polycondensation.

As a composite resin of a polyester resin and a vinyl resin obtained by performing a polycondensation reaction and an addition polymerization reaction in the same reaction vessel in parallel, the polyester resin described above may be used as a raw material of the polycondensation resin. A resin or the like is used, but is not particularly limited as long as a polyester resin is obtained.

The raw material monomer of the addition polymerization resin used in the present invention is typically a monomer which obtains a vinyl resin by radical polymerization, but is not particularly limited. Examples of monomers used for forming the vinyl resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, and p-methylstyrene.
Ethyl styrene, vinyl naphthalene, for example ethylene,
Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene, for example, vinyl esters such as vinyl chloride, vinyl bromide, vinyl acetate and vinyl formate, for example, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid n -Propyl, isopropyl acrylate, tert-butyl acrylate, amyl acrylate,
Methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, amyl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate, methacrylic acid Ethylenic monocarboxylic acids such as dimethylaminoethyl dimethyl, diethylaminoethyl methacrylate and the like, and esters thereof, for example, acrylonitrile, methacrylonitrile, ethylenic monocarboxylic acid substitution products such as acrylamide, and ethylenic dicarboxylic acid such as dimethyl maleate and substitution thereof And vinyl ketones such as vinyl methyl ketone. Further, a crosslinking agent can be added as needed. Examples of the cross-linking agent for addition polymerization monomers include, for example, divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, diallyl phthalate, and the like. Crosslinking agents can be used.

The amount of the crosslinking agent used is 0.05 to 15 parts based on 100 parts of the raw material monomer of the addition polymerization resin.
Parts by weight, more preferably 0.1 to 10 parts by weight.
When the amount is less than 0.05 part by weight, the effect of the crosslinking agent is not obtained. Fifteen
If the amount is more than 100 parts by weight, melting by heat becomes difficult, and when fixing is performed by using heat, the toner becomes defective in fixing.

Further, a polymerization initiator is used when polymerizing the raw material monomer of the addition polymerization resin. For example, 2,2 '
Azobis (2,4-dimethylvaleronitrile), 2,
2′-azobisisobutyronitrile, other azo-based or diazo-based polymerization initiators, or peroxide polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, and 2,4-dichlorobenzoyl peroxide. . These may be used as a mixture of two or more polymerization initiators for the purpose of adjusting the molecular weight and molecular weight distribution of the polymer. The amount of the polymerization initiator used is based on 100 parts of the raw material monomer of the addition polymerization resin,
It is 0.05 to 15 parts by weight, more preferably 0.5 to 10 parts by weight.

In the present invention, in order to obtain a resin in which the condensation polymerization resin and the addition polymerization resin are chemically bonded, it is preferable to carry out polymerization using a compound which can react with any of the monomers of both resins. Examples of such amphoteric monomers include compounds such as fumaric acid, acrylic acid, methacrylic acid, maleic acid, and dimethyl fumarate.

The amount of the amphoteric monomer used is 2 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts of the raw material monomer of the addition polymerization resin. When the amount is less than 2 parts by weight, the dispersion of the colorant and the charge controlling agent is poor, and the image quality such as background stain is deteriorated. If the amount is more than 20 parts by weight, there is a problem that the resin gels.

In the composite resin as described above, the progress and completion of both reactions need not be simultaneous, and the progress of the reaction can be completed independently by selecting the respective reaction temperature and time. For example, in a reaction vessel, a mixture of a polycondensation raw material monomer of a polyester resin and a mixture of an addition polymerization raw material monomer and a polymerization initiator are dropped and mixed in advance. And then raising the reaction temperature to complete the polycondensation reaction comprising the polyester resin by the polycondensation reaction. According to this method, two types of resins can be effectively dispersed by allowing two independent reactions to proceed in a reaction vessel in parallel.

In the present invention, as the resin component in the toner, a resin other than the above-mentioned resins may be used in combination as long as the performance of the toner is not impaired for the purpose of increasing productivity. In this case, examples of usable resins include the following, but are not limited thereto. Polyurethane resin, silicone resin, ketone resin,
Petroleum resin, hydrogenated petroleum resin. These resins are not limited to being used alone, and may be used in combination of two or more.
Also, these production methods are not particularly limited,
Any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

The oxysalicylic acid compound used in the present invention is represented, for example, by the following formulas (1) and (2).

[0039]

Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ are preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an allyl group. R ₁ ,
R ₂ , R ₃ and R ₄ may be the same or different at the same time. R ₁ and R ₂ , R ₂ and R ₃ or R ₃ and R ₄ may form an aromatic ring or an aliphatic ring which may have a substituent group by bonding. M represents a metal, m is an integer of 3 or more, and n is an integer of 2 or more.

[0040]

Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
N, S, O, or a hetero atom of P may be included, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond,
R ₂ and R ₃ each independently represent an alkyl group, an alkenyl group,
Alkoxy group, aryl group or aryloxy group or aralkyl group or aralkyloxy group which may have a substituent, halogen group, hydrogen, hydroxyl group, amino group which may have a substituent, carboxyl group, carbonyl group, nitro group Group,
A nitroso group, a sulfonyl group, a cyano group, R ₄ represents a hydrogen or an alkyl group, l is an integer of 0 or 3 to 12, m is an integer of 1 to 20, n is an integer of 0 to 20,
o is an integer from 0 to 4, p is an integer from 0 to 4, q is an integer from 0 to 3, r is an integer from 1 to 20, and s is an integer from 0 to 20. As the central metal M of the metal compound of the present invention, any metal having a valence of 3 or more can be used, and Fe, Ni, Al, Ti
And Zr are preferable, and Fe is particularly preferable from the viewpoint of safety for the human body.

As the colorant, any known colorants can be used. As the black colorant, for example, carbon black, aniline black, furnace black, lamp black and the like can be used. As the cyan coloring agent, for example, phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, ultramarine blue and the like can be used.
As the magenta colorant, for example, rhodamine 6G lake, dimethylquinacridone, watching red, rose bengal, rhodamine B, alizarin lake, and the like can be used. As the yellow colorant, for example, chrome yellow, benzidine yellow, Hanza yellow, naphthol yellow, molybdenum orange, quinoline yellow, tartrazine and the like can be used.

As the release agent used in the present invention, any conventionally known release agents such as montan wax, oxidized rice wax, solid silicone varnish, higher fatty acid higher alcohol and low molecular weight polypropylene wax are used alone or in combination. Can be used. In particular, the free fatty acid-type carnauba wax is preferable because its effect is greatest in this combination. This is to react with the highly reactive part of the wax and create a lightly crosslinked structure,
It is considered that there is an effect of improving hot offset resistance. Carnauba wax is preferably a microcrystalline wax, and preferably has an acid value of 5 or less and a particle diameter of 1 μm or less when dispersed in a toner binder. The amount of these release agents used is 1 to 1 with respect to the toner resin component.
20 parts by weight, more preferably 3 to 10 parts by weight. The volume average particle size of the release agent before being dispersed in the toner binder is preferably from 10 to 800 μm. If it is less than 10 μm, the dispersion diameter in the toner binder is too small to have a sufficient diameter-releasing effect, causing an offset problem. When the average particle diameter exceeds 800 μm, the dispersion diameter in the toner binder becomes large, and the precipitation of the release agent on the toner surface becomes large, which causes problems due to fluidity and sticking to the inside of the developing machine. The particle size was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.

The charge control agent contained in the toner used in the present invention can be used in combination with a conventionally known charge control agent. As the negative charge control agent, a fluorinated quaternary ammonium chloride, a metal salt of a monoazo dye,
Naphthoic acid, a metal complex of dicarboxylic acid, and the like. In particular, by containing a metal salt of a monoazo dye, the occurrence of fogging and the like is further reduced, and a good image can be obtained over a long period of time.

Further, the toner of the present invention further contains a magnetic material and can be used as a magnetic toner. As the magnetic material contained in the magnetic toner of the present invention, magnetite,
Metals such as iron oxide, iron, cobalt, nickel such as hematite and ferrite, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium , Tungsten, and alloys of metals such as vanadium and mixtures thereof. These ferromagnetic materials have an average particle size of 0.1 to 2 μm.
and about 20 to 200 parts by weight, particularly preferably 40 to 100 parts by weight, based on 100 parts by weight of the resin component.
It is 150 parts by weight.

Further, the toner of the present invention may optionally contain additives. Examples of the additive include a lubricant such as Teflon (registered trademark) and zinc stearate, or a polishing agent such as cerium oxide and silicon carbide; a fluidity imparting agent such as colloidal silica and aluminum oxide; a caking inhibitor; Examples include a conductivity-imparting agent such as black and tin oxide, and a fixing aid such as low-molecular-weight polyolefin.

The toner of the present invention may be used as a one-component developer toner or a two-component developer. Further, when the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder. As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, powder having magnetic properties such as nickel powder, glass beads, and the like, and the surfaces thereof are made of resin or powder. Coatings and the like can be mentioned.

The resin that can be coated on the carrier in the present invention includes a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluororesin, a polyester resin, an epoxy resin and the like. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, when the styrene content is less than 30% by weight, the developing characteristics are low, and when the styrene content exceeds 90% by weight, the coating film becomes hard and easily peels off, shortening the life of the carrier. In addition, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive material, a charge control agent, and the like, in addition to the above resin.

Regardless of whether the toner of the present invention is used as a one-component developer or a two-component developer, the toner is filled in a container, and the container filled with the toner is distributed separately from the image forming apparatus. In general, a user mounts an image on an image forming apparatus to form an image. What is used as the container is not limited, and is not limited to a conventional bottle type or cartridge type. The image forming apparatus is not limited as long as it is an apparatus for forming an image by electrophotography, and includes, for example, a copying machine and a printer.

[0049]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an example of an image forming apparatus according to the present invention will be described with reference to the drawings. FIG. 1 shows an example of an image forming apparatus in which a container filled with the electrophotographic developer of the present invention is mounted, and a developing unit (101) mounted in an image forming apparatus main body; FIG. 4 is a partial cross-sectional view showing a developer container (102) filled with the electrophotographic developer of the present invention to be supplied to the developing section (101), and a developer feeding means (103) for connecting the two. .

In FIG. 1, a developing section (101) is a developing housing filled with the electrophotographic developer of the present invention containing a liquid two-component developer (D) formed by mixing a toner and a carrier. (104) and first and second stirring screws (105) for stirring and mixing the developer (D).
6) and a developing roller (107), and the developing roller (107) is a photoconductor (108) of a latent image carrier.
Are arranged to face each other. The photoconductor (108) is driven to rotate in the direction indicated by the arrow, and an electrostatic latent image is formed on the surface thereof. Reference numeral (126) in the figure denotes a cap fitted on the connecting member (124) with or without the filter (125). Around the photoconductor (108), a charging unit, an exposure unit, a transfer unit, a charge removing unit (not shown)
Other known units such as a cleaning unit are arranged.

The first and second stirring screws (10
5) As the (106) rotates, the developer (D) in the developing housing (104) is agitated, and the carrier of the developer is frictionally charged to the opposite polarity. The developer (D) is supplied to the peripheral surface of a developing roller (107) driven to rotate in the direction of the arrow, and the supplied developer is carried on the peripheral surface of the developing roller (107). By the rotation of 107), the sheet is conveyed in the rotation direction. Next, the amount of the conveyed developer is regulated by the doctor blade (109), and the regulated developer is carried to a developing area between the photoconductor (108) and the developing roller (107). The toner in the developer is electrostatically transferred to the electrostatic latent image on the photoreceptor surface, and the electrostatic latent image is visualized as a toner image. FIG. 2 is a schematic sectional view showing an example of the color electrophotographic copying apparatus. In FIG. 2, a color image reading device (1) reads an image of a document (3) through an illumination lamp (4), a group of mirrors (5a), (5b), (5c) and a lens (6) and a color sensor ( 7), the color image information of the original is read for each color separation light of blue (hereinafter, referred to as B), green (hereinafter, referred to as G), and red (hereinafter, referred to as R), and converted into an electric image signal. I do. Then, based on the B, G, and R color-separated image signal intensity levels, an image processing unit (not shown) performs color conversion processing to obtain black (hereinafter, referred to as Bk), cyan (hereinafter, referred to as C), Magenta (hereinafter referred to as M) and yellow (hereinafter referred to as Y) color image data are obtained.

Based on the color image data, a full-color toner image is formed on the transfer sheet as follows. In the color image recording apparatus (2) of FIG. 2, the electrophotographic photosensitive member (9) rotates counterclockwise as indicated by an arrow, and around the photosensitive member cleaning unit (including a pre-cleaning neutralizer) (10). ), Static elimination lamp (11), charger (12), potential sensor (13), black developing unit (14), cyan developing unit (15), magenta developing unit (16), yellow developing unit (1)
7), an optical sensor (1
8), an intermediate transfer belt (19) and the like are arranged.
Further, each developing unit includes a developing sleeve that rotates by bringing a spike of developer into contact with the surface of the photoreceptor (9) to develop an electrostatic latent image, and a developing paddle that rotates to draw up and agitate the developer. And developer toner concentration sensor (14
c), (15c), (16c) and (17c). Each developing unit is loaded with an electrophotographic developer.

The black image data is sent to the color image recording device (2), the writing optical unit (8) converts the black image data into an optical signal, and the charged electrophotographic photosensitive member (9) is irradiated with a laser beam. By performing optical writing, an electrostatic latent image of a black image is formed on the electrophotographic photoreceptor (9) (for example, image portions -80V to -13).
0 V, non-image part -500 V to -700 V). The electrostatic latent image of the black image is developed by the black toner on the developing sleeve which has started rotating before the leading end of the electrostatic latent image reaches the developing position of the black developing unit (14). A black toner image is formed on the photoreceptor (9). When the rear end of the electrostatic latent image has passed the developing position, the developing unit (14) is evacuated to a state where development is not performed.

The black toner image formed on the electrophotographic photosensitive member (9) is transferred onto the surface of the intermediate transfer belt (19) driven at the same speed as the photosensitive member (9) by the intermediate transfer belt unit described below. Transcribed. In FIG. 2, the intermediate transfer belt (19) is stretched around a drive roller (21), a transfer bias roller (20a), a ground roller (20b), and a group of driven rollers, and is driven and controlled by a drive motor.

As the intermediate transfer belt (19), for example, a fluorocarbon resin ETFE (ethylene
Tetrafluoroethylene) and the like, and those having a volume resistivity of 10 ⁹ Ωcm or less are preferable. As the transfer bias roller (20a), for example, a hydrin rubber roller is coated with a PFE tube, and the volume resistivity is 10 ^9.
Ωcm or the like can be used. Further, as the earth roller (20b), for example, a roller grounded in a roller shaft can be used.

From the photoreceptor (9) to the intermediate transfer belt (19)
The transfer of the toner image to the transfer bias roller (20a) is performed by applying a predetermined bias voltage to the transfer bias roller (20a) in a state of close contact between the photoconductor (9) and the intermediate transfer belt (19). The photoreceptor (9) and the intermediate transfer belt (1
9) is in contact with the transfer bias roller (20).
This is performed by pressing the intermediate transfer belt (19) against the photoreceptor (9) with the a) and the earth roller (20b).

The intermediate transfer belt (19) is grounded by an earth roller (20b), so that the area affected by the electric field generated by the transfer bias applied by the transfer bias roller (20a) is affected by the photosensitive member (9). ) And the intermediate transfer belt (19) can be set within a range in which the intermediate transfer belt (19) is in close contact. Thereby, the intermediate transfer belt (1
9) It is possible to prevent the action of the electric field on the toner image on the photoreceptor before the contact, so that the increase in the interval between toner particles due to the transfer bias electric field is prevented, and the generation of voids in the toner image is prevented. can do.

The black toner image is transferred to the intermediate transfer belt (1).
After being transferred to 9), the electrophotographic photoreceptor (9) is cleaned by a photoreceptor cleaning unit (10),
After the charge is uniformly removed by the charge removing lamp (11), it is charged by the charger (12). Next, the cyan image data is sent to the color image recording device (2), the writing optical unit (8) converts the cyan image data into an optical signal, and light-writes the charged electrophotographic photosensitive member (9) with laser light. Is performed, an electrostatic latent image of a cyan image is formed on the electrophotographic photosensitive member (9).

The electrostatic latent image of the cyan image is developed by a cyan developing unit (15) which operates in the same manner as the black developing unit (14), and a cyan toner image is formed on the electrophotographic photosensitive member (9). You. The cyan toner image formed on the electrophotographic photoreceptor (9) is aligned with the black toner image already transferred to the intermediate transfer belt (19), and the intermediate transfer belt (19) is adjusted in the same manner as in the case of the black toner image. ) Is transferred to the surface. Thereafter, similarly, the magenta toner image and the yellow toner image are sequentially aligned and transferred to the surface of the intermediate transfer belt (19), whereby a full-color toner image is formed on the intermediate transfer belt (19).

The full-color toner image formed on the intermediate transfer belt (19) is transferred onto a transfer sheet as follows. In FIG. 2, the intermediate transfer belt (19)
A transfer unit (23) for transferring a toner image from a transfer sheet to a transfer sheet includes a transfer bias roller, a roller cleaning blade, a mechanism for contacting and separating from a belt, and the like. The bias roller is normally separated from the surface of the belt (19), but is pressed by the contact / separation mechanism in a timely manner when transferring the full-color toner image formed on the intermediate transfer belt (19) to the transfer sheet. Then, a predetermined bias voltage is applied. Thereby, the full-color toner image formed on the intermediate transfer belt (19) is transferred to the transfer sheet.

As shown in FIG. 2, the transfer sheet (2
4) is fed by the feed roller (25) and the registration roller (26) at the timing when the leading end of the full-color toner image formed on the intermediate transfer belt reaches the transfer position on the transfer sheet. You. The belt cleaning unit (22) is composed of a brush roller, a rubber blade, a mechanism for contacting and separating from the belt, and the like, while the toner images of each color are transferred onto the intermediate transfer belt (19). After the toner image is transferred from the intermediate transfer belt (19) to the transfer sheet, the cleaning unit (22) is pressed against the intermediate transfer belt (19) by a contact / separation mechanism, thereby The surface is cleaned.

As shown in FIG. 2, the transfer sheet on which the full-color toner image has been transferred is conveyed to a fixing device (28) by a conveyance unit (27), and is heated by a fixing roller (28a) controlled to a predetermined temperature. The full-color toner image is fixed by the pressure roller (28b). In the fixing step, it is preferable to use a fixing method using a fixing roller for fixing by supplying heat at the same time as applying pressure. Note that the temperature of the fixing roller is preferably set to 160 ° C. to 190 ° C. Further, in order to prevent fusion of the toner to the fixing roller, a method of applying a release agent such as silicone oil to the fixing roller is also effective. Fixing roller set temperature is 160
If the temperature is lower than ℃, the toner is not softened smoothly, leaving voids. If the temperature is set higher than 190 ° C., the heat supply of the fixing roller may not follow in continuous copying. The preferred set temperature of the fixing roller is 170 ° C. to 185 ° C., depending on the process speed. With this temperature setting, there is little variation in the fixing roller temperature in continuous copying, so that a fixed quality fixed toner image can be obtained.

In the above description, a case where a full-color toner image is obtained by four-color mode color image data of black, cyan, magenta, and yellow has been described.
Also in the three-color mode and the two-color mode, it is possible to form an electrostatic latent image based on a designated color, operate the developing unit for that color, and form a toner image on the transfer sheet in the same manner as described above. it can. When a single-color toner image is formed on a transfer sheet, only the developing unit for that color is set to the operating state, and the intermediate transfer belt (19) is driven while being in contact with the electrophotographic photosensitive member (9). Further, the image forming operation can be performed while the cleaning unit (22) is still in contact with the intermediate transfer belt (19).

[0064]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. All parts are parts by weight. Next, a production example of a carrier having a silicone resin in a coating layer will be described.
These can be performed by known means. [Carrier production example] Composition of coating layer forming liquid Silicon resin solution 100 parts (RSR213 manufactured by Dow Corning Silicone Toray Co., Ltd.) Carbon black 1 part Silane coupling agent 2 parts The above formulation is dispersed with a homomixer for 30 minutes to form a coating layer. A forming solution was prepared. This coating layer forming solution is mixed with ferrite particles 10
A carrier having a coating layer formed on a surface of 00 parts by weight using a fluidized bed type coating apparatus was obtained.

[Production Example of Resin] Production Example of Nonlinear Polyester Resin Fumaric acid: 10 mol, trimellitic anhydride: 4 mo
1, Bisphenol A (2,2) propylene oxide: 6 mol, Bisphenol A (2,2) ethylene oxide: 4 mol were placed in a flask equipped with a stainless steel stirrer, a falling condenser, a nitrogen gas inlet tube and a thermometer, and a nitrogen atmosphere was added. The polycondensation reaction was carried out while stirring at a temperature of 220 ° C. under the conditions to obtain a non-linear polyester resin 1.

Production Example of Linear Polyester Resin Terephthalic acid: 8 mol, trimellitic anhydride: 3 mol
1, Bisphenol A (2,2) propylene oxide: 6 mol, Bisphenol A (2,2) ethylene oxide: 4 mol were placed in a flask equipped with a stainless steel stirrer, a falling condenser, a nitrogen gas inlet tube and a thermometer, and a nitrogen atmosphere was added. The polycondensation reaction was carried out while stirring at a temperature of 220 ° C. under the conditions to obtain a linear polyester resin 1.

Production Example of Composite Resin 20 mol of styrene as an addition polymerization reaction monomer, 5 mol of butyl methacrylate, and 0.4 mol of t-butyl hydroperoxide as a polymerization initiator were placed in a dropping funnel. 10 mol of fumaric acid, 4 mol of trimellitic anhydride as polycondensation reaction monomer, 6 mol of bisphenol A (2.2) propylene oxide, bisphenol A (2
2) Ethylene oxide: 4 mol, and 60 mol of dibutyltin oxide as an esterification catalyst were placed in a flask equipped with a stainless steel stirrer, a falling condenser, a nitrogen gas inlet tube and a thermometer, and 135 ° C. under a nitrogen atmosphere.
While stirring with, a mixture obtained by previously mixing the addition polymerization-based raw materials was dropped from the dropping funnel over 5 hours. 13 after the end
After aging for 6 hours while maintaining the temperature at 5 ° C., the temperature was raised to 220 ° C. and the reaction was carried out to obtain a composite resin 1.

[Production Example of Oxycarboxylic Acid Compound] (Synthesis Example 1) 3,5-di-t-butylsalicylic acid 3mo
1 and caustic soda are dissolved in water and stirred at 60 ° C.
Crystals were obtained by dropwise addition of a 1.5 mol aqueous solution of ferric chloride (FeCl ₂ ). The crystals were filtered, washed, dried and pulverized to obtain a dark powder (compound 1). The formula (Compound 1) is shown below.

[0069]

Embedded image

Synthesis Example 2 4 mol of 3,5-di-t-butylsalicylic acid and caustic soda were dissolved in water, and 1 mol of zirconium chloride (ZrCl ₂ ) was stirred at 50 ° C.
Crystals were obtained by dropwise addition with an aqueous solution. The crystals were filtered, washed, dried and pulverized to obtain a white powder (compound 2). The formula (Compound 2) is shown below.

[0071]

Embedded image

(Synthesis Example 3) 5 mol of 3,5-di-t-butylsalicylic acid and caustic soda were dissolved in water, and zirconium oxychloride (ZrOCl _2.
8H ₂ O) 4 mol aqueous solution was added dropwise to obtain crystals. The crystals were filtered, washed, dried and pulverized to obtain a white powder (compound 3). The formula (Compound 3) is shown below.

[0073]

Embedded image

(Example 1) Non-linear polyester resin 1 (hydroxyl value 35 mg KOH / g) 100 parts Molecular weight distribution (peak 6000 half width 70,000) Low molecular weight polypropylene (Viscol 550P manufactured by Sanyo Chemical) 3 parts Carbon black (Mitsubishi Chemical Corporation) MA-100) 8 parts Compound 1 1 part After sufficiently stirring and mixing the mixture having the above composition in a Henschel mixer, the mixture was rolled at 130 to 140 ° C. at a temperature of 130 to 140 ° C. for about 3 hours.
After heating and melting for 0 minutes and cooling to room temperature, the obtained kneaded material was roughly pulverized to 200 to 400 μm with a hammer mill,
Using a jet stream to directly impinge the coarsely pulverized material on the impingement plate and pulverize the finely pulverized powder obtained by the finely pulverized device obtained by the finely pulverized device into a classification chamber, and centrifugally separate the pulverized material. Pulverization and classification were carried out by an IDS-2 type pulverization and classification apparatus (manufactured by Nippon Pneumatic Industries, Ltd.) having an integrated air classifier to obtain a toner having a volume average particle diameter of 10.0 μm. To 99 parts of the toner, 1.0 part of an additive (R972 manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was stirred and mixed by a Henschel mixer. 2.5 parts of this toner and 97.5 parts of a carrier were mixed by a ball mill to obtain a developer.

(Example 2) A toner similar to that of Example 1 was obtained except that compound 1 of example 1 was changed to compound 3.

Example 3 The same procedure as in Example 2 was carried out except that the low-molecular-weight polypropylene (Viscol 550P manufactured by Sanyo Kasei) in Example 2 was changed to a defatty acid type carnauba wax (WA03: Toa Kasei Co., Ltd.). A toner was obtained.

(Example 4) Non-linear polyester resin 1 (hydroxyl value 35 mg KOH / g) 50 parts Molecular weight distribution (peak 6000 half width 70,000) Linear polyester resin 1 (hydroxyl value 40 mg KOH / g) 35 parts Molecular weight distribution (peak 5000 half-value width 10000) Composite resin 1 5 parts Molecular weight distribution (peak 5500 half-value width 60000) De-free fatty acid type carnauba wax (WA03: Toa Kasei Co., Ltd.) 3 parts Carbon black (Mitsubishi Chemical Corporation MA-100) 8 parts Compound 1 1 part After sufficiently stirring and mixing the mixture having the above composition in a Henschel mixer, about 3 parts at a temperature of 130 to 140 ° C. with a roll mill.
After heating and melting for 0 minutes and cooling to room temperature, the obtained kneaded material was roughly pulverized to 200 to 400 μm with a hammer mill,
Using a jet stream to directly impinge the coarsely pulverized material on the impingement plate and pulverize the finely pulverized powder obtained by the finely pulverized device obtained by the finely pulverized device into a classification chamber, and centrifugally separate the pulverized material. Pulverization and classification were carried out by an IDS-2 type pulverization and classification apparatus (manufactured by Nippon Pneumatic Industries, Ltd.) having an integrated air classifier to obtain a toner having a volume average particle diameter of 10.0 μm. The molecular weight distribution of the toner was measured by GPC and found to have a peak of about 6,500 and a half width of about 20,000. To 99 parts of the toner, 1.0 part of an additive (R972 manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was stirred and mixed by a Henschel mixer. 2.5 parts of this toner and 97.5 parts of a carrier were mixed by a ball mill to obtain a developer.

Example 5 A toner similar to that of Example 4 was obtained in the same manner as in Example 4 except that the resin ratio was changed. When the molecular weight distribution of the toner was measured by GPC,
The peak was about 5,500 and the half width was about 12,000.

Example 6 A toner similar to that of Example 6 was obtained except that the volume average particle diameter of Example 5 was changed to 7.0 μm.

Example 7 A toner similar to that in Example 7 was obtained except that the kneaded toner obtained in Example 5 was pulverized by a mechanical pulverizer.

(Comparative Example 1) The hydroxyl value of the nonlinear polyester resin of Example 1 was changed from 35 mgKOH / g to 28 mgKOH.
/ G except that the toner was changed to / g.

Comparative Example 2 The hydroxyl value of the non-linear polyester resin of Example 1 was changed from 35 mg KOH / g to 71 mg KOH.
/ G except that the toner was changed to / g.

(Comparative Example 3) Compound 1 of Example 1 was replaced with 3,5
A toner similar to that of Example 1 was obtained except that the composition was changed to a Zn-II-di-t-butylsalicylate compound (Bontron E-84, manufactured by Orient Chemical Industries).

Comparative Example 4 A toner similar to that of Example 1 was obtained except that Compound 1 of Example 1 was changed to an iron-containing azo complex (T77 manufactured by Hodogaya Chemical Co., Ltd.).

The evaluation of each toner was performed as follows. (Charge rising property) Using a ball mill stirrer, a charge amount A ₁ after 1 minute and a charge amount A ₂ after 10 minutes by a blow-off method.
Was measured. The charge rising property was determined using the following equation, and evaluated in five steps according to the following criteria.

[0086]

## EQU1 ## Charging start-up property = (A ₂ −A ₁ ) / 9 good ：: less than 0.1, ：: 0.1 to 0.25, □: 0.25 to 0.5, Δ: 0.5 -0.75, ×: 0.75 or more bad

(Environmental Stability) Environmental stability is 10 ° C., 2
The amount of charge in a low-temperature and low-humidity environment of 0% and a high-temperature and high-humidity environment of 30 ° C. and 80% is obtained by a blow-off method, and the value at that time is substituted into the following equation. Was evaluated on a five-point scale.

[0088]

[Equation 2] Environmental fluctuation rate (%) = (low-temperature low-humidity charge amount-high-temperature high-humidity charge amount) / low-temperature low-humidity charge amount × 100 good ：: less than 50%, ：: 50-60%, □: 60-70% , Δ: 70-80%, ×: 80% or more

(Evaluation of Fixing Property) Copier MF-2 manufactured by Ricoh Co., Ltd. using a Teflon roller as a fixing roller.
Using a modified apparatus of the fixing section No. 00, Ricoh type 6200 paper was set in this apparatus and a copying test was performed.
The fixing temperature was changed and three images were printed at each temperature to determine the offset occurrence temperature. The evaluation conditions of the hot offset were as follows: the linear speed of the paper feed was 50 mm / sec, and the surface pressure was 2.0 K
The evaluation conditions of gf / cm ² , nip width 4.5 mm, and cold offset were as follows.
c, the surface pressure was set to 1.2 kgf / cm ² , and the nip width was set to 3 mm.

The hot offset occurrence temperature and the low temperature offset occurrence temperature were determined as follows. (Hot offset) Good ：: 201 ° C. or more, ：: 200 to 191 ° C., □: 190 to 181 ° C., Δ: 180 to 171 ° C., ×: 170 ° C. or less Bad (Low temperature offset) Good ◎: Less than 125 ° C., ○ : 125 to 135 ° C, □: 135 to 145 ° C, Δ: 145 to 155 ° C, ×: 155 ° C or more.

(Evaluation of pulverizability) A toner pulverized to an average particle size of 1 mm or less was used as an ID of Nippon Pneumatic Co., Ltd.
It was determined from the amount of processing per unit time when pulverized under a certain condition with an S-2 type pulverizer, and evaluated according to criteria. (Good) ：: 7 kg or more, ：: 7 to 5 kg, □: 5 to 3 kg, Δ: 3 to 2 kg, ×: Less than 2 kg (bad)

(Evaluation of heat resistance storage stability)
In a 0 ml glass bottle, it was left in a high-temperature bath at 60 ° C. for 4 hours, and then a penetration test (JIS K2235-199).
In 1), the penetration was determined as follows. (Good) ：: 10 mm or more, ：: 9.9 to 5 mm, Δ: 4.9 to 3 mm, ×: 2.9 to 0 mm (bad)

(Fine line reproducibility) Copier M, manufactured by Ricoh Co., Ltd.
Using F-200, an image evaluation test was performed to evaluate fine line reproducibility. The evaluation was performed in five steps according to the following criteria. ◎: Very good, ○: Good, □: Normal, △: Bad, ×: Very bad

(Evaluation of Insect Eating) Copier M manufactured by Ricoh Co., Ltd.
Using the F-200, a copy of the character chart (a line of "machine", 19 characters per line, 10 points, Ming Dynasty) is made on the postcard made by government, and the number of characters missing from the transfer (insect eating) on each line is counted. The relative evaluation was made on the basis of the number of characters of the transfer missing (insect-eating) characters. Good ：: good, □: normal, ×: bad Table 1 shows the evaluation results of each toner.

[0095]

[Table 1-1]

[0096]

[Table 1-2]

[0097]

As apparent from the detailed and specific description, the first object of the present invention is that the first object of the present invention is to have good charge rising property, good environmental stability of charge, and good high-temperature offset resistance. The purpose of the present invention is to provide an image forming toner and an image forming apparatus capable of obtaining high-quality images with good low-temperature offset properties, high productivity, excellent heat-resistant storage stability, and an extremely excellent effect. is there.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of a container filled with an electrophotographic developer of the present invention and an image forming apparatus equipped with the container.

FIG. 2 is a schematic configuration diagram illustrating an example of an image forming method and apparatus according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 101 developing unit 102 developer storage container 103 developer feeding means 104 developing housing 105 stirring screw 106 stirring screw 107 developing roller 108 photoconductor 109 doctor blade 124 connecting member 125 filter 126 cap 501 photoconductor (image carrier) 502 charging roller 503 developing device 504 developer 505 developing sleeve (developer carrier) 506 transfer belt (transfer means) 506a bias roller 507 cleaning blade 508 collection spring 509 collection coil 510 photoconductor and cleaning unit (PCU) 513 transport screw 514 paddle (stirring) Mechanism) 516 reflection density detection sensor (P sensor) 517 toner density sensor 518 registration roller 520 static elimination lamp D developer r image exposure S transfer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Matsuda 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Akemi Sugiyama 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Inside the company Ricoh

Claims (15)

[Claims] 1. An electrostatic charge developing toner comprising at least a binder resin, a colorant and a release agent, wherein the binder resin has a hydroxyl value of 30 mgKOH / g to 70 mgK.
An image forming toner comprising at least a non-linear polyester resin (A) containing OH / g and a metal compound of an aromatic oxycarboxylic acid having a trivalent or higher valent metal. 2. A mixture comprising a non-linear polyester resin (A), a linear polyester resin (B), a raw monomer of a polycondensation resin and a raw monomer of an addition polymerization resin is used as the binder resin. 2. The image forming method according to claim 1, further comprising a composite resin (C) of a polyester resin and a vinyl resin obtained by performing a polycondensation reaction and an addition polymerization reaction in a reaction vessel in parallel. For toner. 3. The image forming toner according to claim 1, wherein the aromatic oxycarboxylic acid satisfies the following structural formula. Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
May contain N, S, O, P heteroatoms, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond,
R ₂ and R ₃ each independently represent an alkyl group, an alkenyl group,
Alkoxy group, aryl group or aryloxy group or aralkyl group or aralkyloxy group which may have a substituent, halogen group, hydrogen, hydroxyl group, amino group which may have a substituent, carboxyl group, carbonyl group, nitro group Group,
A nitroso group, a sulfonyl group, a cyano group, R ₄ represents hydrogen or an alkyl group, l is an integer of 0 or 3 to 12, m is an integer of 1 to 20, n is an integer of 0 to 20,
o is an integer from 0 to 4, p is an integer from 0 to 4, q is an integer from 0 to 3, r is an integer from 1 to 20, and s is an integer from 0 to 20. M is a trivalent or higher metal. ] 4. The image forming toner according to claim 1, wherein the central metal is Fe. 5. The image forming toner according to claim 1, wherein the central metal is Zr. 6. The method according to claim 1, wherein said releasing agent contains carnauba wax of a free fatty acid type.
The image forming toner according to any one of the above. 7. The value of the molecular weight distribution of the toner (mainly the binder resin) determined by GPC determined by the THF-soluble matter of 10
The image forming toner according to any one of claims 1 to 6, wherein the toner has at least a peak between 00 and 10,000, and the half width of the distribution is 15,000 or less. 8. The method according to claim 1, wherein a metal salt of a monoazo dye is contained as a charge controlling agent.
4. The toner for forming an image according to claim 1. 9. The electrostatic charge developing toner according to claim 1, wherein the toner has a volume average particle diameter D _{4 of 4} to 8 μm. 10. The electrostatic charge developing toner according to claim 1, wherein an average circularity of the toner is 0.940 or more. 11. A two-component image forming developer comprising the image forming toner according to claim 1 and a carrier. 12. An image forming toner container filled with the image forming toner according to claim 1. Description: 13. An image forming developer container filled with the two-component image forming developer according to claim 11. 14. An image forming apparatus comprising a container filled with the image forming toner according to claim 12. 15. A developing container for image formation, comprising a container filled with the developer for forming a two-component image according to claim 13.