JPH08234489A - Color toner, two-component developer, image forming device, image forming method and production of color toner - Google Patents

Abstract

PURPOSE: To perform a color image formation with excellent fixing property, color mixing property, triboelectrification property and obtain a color image excellent in gloss, high in image density and saturation, and excellent in transparency by incorporating a specified coloring agent and color toner particles. CONSTITUTION: This color toner contains color toner particles containing at least a coloring agent and nonlinear polyester resin synthesized by using a compd. expressed by formula or its acid anhydride, and the coloring agent consists of pigment particles. The pigment particles in the color toner particles has <=0.7μm number average particle size, in which pigment particles of 0.1-0.5μm particle size are included by >=60 number % and particles of >=0.8μm particle size are included by <=10 number %. The color toner has 85-120 deg.C softening point Tm calculated from the flow tester curve. In formula, (n) is an integer of >=3, R is hydrogen atom, a C1-C18 alkyl group, C2-C18 alkenyl group or C6-C18 aryl group, and respective substituents R may be the same as or different from each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for developing an electrostatic image in electrophotography, electrostatic recording and electrostatic printing, and in particular, the color reproducibility of a color image is wide and the offset resistance is excellent. The present invention also relates to a color toner, a developer for developing an electrostatic image using the color toner, an image forming apparatus, an image forming method, and a color toner manufacturing method.

[0002]

2. Description of the Related Art In recent years, full-color copying machines have begun to attract attention. In particular, a digitalized full-color copying machine has been attracting attention and is being widely deployed in the market.

Color image formation by full-color electrophotography generally reproduces colors by using color toners of three primary colors of yellow, magenta, and cyan, or four colors of black in addition thereto.

In the general color image forming method, the light from the original is formed on the photoconductive layer through a color separation light transmitting filter having a complementary color relationship with the color of the toner. Next, the toner is held on the support through a development and transfer process. The above steps are sequentially performed a plurality of times, and the toners are superposed on the same support while matching the registration,
The final full-color image is obtained by fixing only once.

In the color electrophotographic method which requires development of a plurality of times and superposition of several kinds of toner layers of different colors on the same support as the fixing step, the fixing characteristics that color toners should have. Is an extremely important factor.

That is, the fixed color toner is required to suppress diffused reflection due to toner particles as much as possible and to have an appropriate gloss and gloss.

A color toner having transparency and a wide color reproducibility that does not hinder the toner layers of different color tones under the toner layer.

As a color toner that can satisfy these requirements,
The applicants of the present invention have filed Japanese Patent Application Laid-Open Nos. 50-62442 and 5
Japanese Patent Application Laid-Open No. 1-144625 and Japanese Patent Application Laid-Open No. 59-57256 disclose a combination of a novel binder resin for color toner and a colorant.

The color toners described above have a considerable sharp melt property, and when combined with a silicone rubber roller capable of applying silicone oil, the toner shape changes to a state of almost complete melting at the time of fixing, which is preferable. Glossiness and color reproducibility are obtained.

These effects mean that the viscous term is more important than the elastic term in the viscoelastic characteristic of the binder resin as the fixing characteristic of the toner.

That is, upon heating, the toner behaves more as a viscous material, the heat melting property is increased, and the glossiness is also obtained.

However, such a binder resin design emphasizing the viscosity term inevitably reduces intermolecular agglomeration at the time of heat fusion, and also increases toner adhesion to the heat roller when passing through the fixing device. become. These tend to cause the high temperature offset phenomenon.

In particular, when a silicone rubber roller is used as a fixing roller, if it is repeatedly used regardless of whether or not the release oil is applied, a high temperature offset is likely to occur due to an essential decrease in the releasability of the surface of the silicone rubber roller. At the initial stage of use of the silicone rubber roller, some releasability can be maintained due to the silicone oil impregnated inside the silicone rubber and the smoothness and cleanliness of the roller surface. However, the image area is large like a color image, and the amount of toner held on a support such as plain paper is much larger than that of a black / white copy image.
When copying is continued, naturally the oil in the silicone rubber is depleted, the roller surface also becomes rough, and the releasability of the roller gradually decreases. The speed of deterioration of the releasability reaches several times that of black and white copying.

Further, since the toner itself has almost no elasticity as described above, the anti-offset effect is low. As a result, a toner coating or granular deposits are formed on the surface of the fixing roller after a few thousand to tens of thousands of sheets, and the toner upper layer portion of the image surface is peeled off when passing through the heat roller. So-called high temperature offset occurs.

Various measures have been attempted with toners in order to solve or alleviate the above problems, but further improvements are desired. For example, JP-A-55-60960, JP-A-57-208559, and JP-A-58-1195.
No. 3, JP-A-58-14144 and JP-A-SHO-6
As described in JP-A-0-123852, a method of adding low-molecular-weight polyethylene, polypropylene, wax, higher fatty acid, etc., which is a releasable component, to the toner is also used in order to increase the releasability. These methods are effective in preventing offset, but on the other hand, if a large amount of them is sufficiently effective in offset resistance, the compatibility with the main binder resin becomes poor, and, for example, the transparency of the OHP image of the color toner becomes poor. It is difficult to call it sufficient, because adverse effects such as: damage; instability in charging characteristics; deterioration in durability;

Japanese Patent Laid-Open Nos. 47-12334 and 5
In JP-A 7-37353 and JP-A-57-208559, an etherified bisphenol monomer,
A non-linear copolymer obtained from a monomer component containing a dicarboxylic acid monomer and a trivalent or higher polyhydric alcohol monomer and / or a trivalent or higher polyvalent carboxylic acid monomer A toner containing a polyester as a binder has been proposed. This technology is based on a polyester composed of an etherified bisphenol monomer and a dicarboxylic acid monomer, which is a trivalent or higher polyvalent alcohol monomer and / or a trivalent alcohol. A polyester obtained by crosslinking with a large amount of a monomer component containing the above polycarboxylic acid monomer is contained as a binder to give the toner anti-offset performance. However, these toners have a slightly high softening point, and therefore, it is difficult to perform good low-temperature fixing, and when used for full-color copying, high-temperature offset resistance is at a practically practical level. However, as described above, the fixability and the sharp melt property are poor, and therefore the color mixing property and the color reproducibility due to the superposition of full-color toners using the polyester are not sufficient. JP-A-57-109825, JP-A-62-
No. 78568, JP-A-62-78569, and JP-A-59-7960 and JP-A-59-29256 by the present applicant, an etherified bisphenol monomer and a long-chain aliphatic monomer are used. Hydrocarbon-introduced dicarboxylic acid monomer or other dicarboxylic acid monomer and 3
A non-linear copolymer obtained from a monomer component containing a polyhydric alcohol monomer having a valence of 3 or more and / or a polycarboxylic acid monomer having a valence of 3 or more, the side chain of which has 3 carbon atoms. Disclosed is a toner containing as a binder a polyester having -22 saturated or unsaturated aliphatic hydrocarbon groups.
These polyester resins are mainly intended for high-speed copying toners.The viscoelastic properties of the resin are, contrary to the above-mentioned viscous polyester, strengthen the elasticity and remarkably prevent high temperature offset to the roller. It has been lowered. At the time of fixing, the pressure and heat of the heat roller are increased as much as possible, and the toner is pressed in a semi-molten state between the fibers of the transfer paper to perform pressure and heat fixing, thereby achieving the object. is there.

Therefore, the toner layer necessary for color copying cannot be melted to form a continuous film and a smooth surface can hardly be obtained, and the fixed toner exists in a particle state on the transfer paper to obtain a color obtained. The image is dull and the saturation is poor. In an OHP image, light is scattered and diffused on the surface of toner particles, almost no light is transmitted, and it becomes practically unusable.

The present applicants proposed in JP-A-2-73366 and JP-A-1-224767 a new polyester resin which is excellent in high temperature offset resistance and can be applied to color copying. Although the resin is superior to the conventional resin for color toners, the effect of preventing the offset to the fixing roller is exhibited at most about 20,000 copies repeatedly and the offset preventing effect of the black and white toner is 100,000. Although the number of sheets is sufficient, it is preferable to further improve the performance in view of the fact that it is required to have printing durability and offset resistance of several hundred thousand sheets at present. In terms of electrification, the polyester has a large difference in electrification amount between a low temperature and low humidity environment and a high temperature and high humidity environment, and the density tends to be slightly lower on the low humidity side in a color image after repeated copying. Scattering and fog may occur.

JP 62-195676 A, JP 62-195678 A and JP 62-19568 A.
No. 0 discloses a polyester resin in which the ratio between the hydroxyl value and the acid value is specified, but these polyester resins are also intended for high-speed fixing, and according to the study by the present inventors, etc. The color toner using the resin has not reached the point where a sufficient color mixing property is obtained.

As a problem peculiar to color copying, at least 3
Color toners of four colors, preferably four color balances, must be in harmony, and it is meaningless to discuss fixing characteristics and color reproducibility of only one color. It is necessary to design and select the resin in consideration of the above.

In principle, if there are three primary colors, yellow, magenta, and cyan, it should be possible to reproduce almost all colors by the subtractive color mixing method.
Therefore, the full-color copying machines on the market at present have a structure in which color toners of three primary colors are overlapped and used. This should ideally be able to achieve all color tones in all density ranges, but in reality, there are still points to be improved such as spectral reflectance characteristics of toner, mixability at the time of overlapping and fixing toner, and decrease in saturation. have.

When a black color is obtained by superimposing three colors, a toner layer three times as much as that of a monochromatic color is formed on the transfer paper, and further it is difficult for the offset resistance.

On the other hand, the demand for the quality of full-color copied images is increasing more and more. For general users who consider printing, full-color copy images are still not at a satisfactory level, and they want a level closer to printing and a level closer to photography. That is, a solid image in a wide image area in a copied image, uniformity of a halftone image, a toner having an image density output covering a wide dynamic range from high density to low density, an OHP image having transparency equivalent to printing, and For example, the transparency of the toner used for that purpose.

The shortest and preferred method to meet these requirements is to first improve the dispersibility of the colorant present in the toner.

JP-A-61-117565 and JP-A-61-156054 disclose a method in which a binder resin, a colorant, a charge control agent and the like are previously dissolved in a solvent and the solvent is removed to obtain a toner. However, they have the problems that it is difficult to control the dispersibility of the charge control agent; that the solvent remains in the final product toner and gives an unpleasant odor.

Japanese Unexamined Patent Publication (Kokai) No. 61-91666 discloses a toner manufacturing method using a halogen-based solvent.
Since the halogen-based solvent has a strong polarity, there is a problem that the colorant used is limited.

JP-A-4-39671 and JP-A-4-39671
In Japanese Patent No. 39672 and Japanese Patent Laid-Open No. 4-242752, a method for producing a toner while applying heat and pressure in a kneader is disclosed. The molecular chain of the constituent binder resin is broken by a strong kneading load, and the partial reduction of the molecular weight in the polymer is promoted. Therefore, high temperature offset is likely to occur in the fixing process. Particularly in color copying, since the toners of three or four colors are laminated and fixed, the latitude of high temperature offset resistance is much more severe than that of black and white toner, and the small number of molecules in the polymer. Cutting easily causes high temperature offset.

In Japanese Unexamined Patent Publication (Kokai) No. 5-34978, a resin and an aqueous presscake of a pigment are charged into a kneader and kneaded by heating to achieve the dispersion of the pigment in the resin. Although it is preferable for dispersion, it does not mention the characteristics of the resin at all, and it is highly pigmented using a resin designed to improve the dispersibility of the pigment during kneading as well as the fixability and offset resistance of the present invention. The toner of the present invention is intended to achieve both the offset resistance and the fixability, which have been difficult until now, and the improvement of the color reproducibility at the same time, by increasing the dispersibility of the toner to a desired pigment dispersion particle size. The contents of are different.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color toner having good fixability and color mixing property, a two-component developer having the color toner, an image forming apparatus having the color toner, and the color toner. An object of the present invention is to provide an image forming method and a method for producing the color toner.

Further, an object of the present invention is to provide a color toner having sufficient triboelectric chargeability, a two-component developer having the color toner, an image forming apparatus having the color toner, and an image forming method using the color toner. And a method for producing the color toner.

Furthermore, an object of the present invention is to provide a high gloss color toner capable of significantly improving the image quality,
A two-component developer having the color toner, an image forming apparatus having the color toner, an image forming method using the color toner, and a manufacturing method of the color toner.

Still another object of the present invention is to provide a color toner in which high-temperature offset is sufficiently prevented and which has a wide fixing temperature range, a two-component developer having the color toner, an image forming apparatus having the color toner, and An object of the present invention is to provide an image forming method using a color toner and a manufacturing method of the color toner.

Still further, an object of the present invention is to provide a color toner which maintains the offset resistance even after repeated fixing paper passages and is less likely to wrap around a fixing roller, a two-component developer containing the color toner, An image forming apparatus having a color toner, an image forming method using the color toner, and a manufacturing method of the color toner.

Still further, an object of the present invention is to
That is, a color toner that is less likely to cause toner fusion to parts such as a developing sleeve, a blade, and a coating roller, a two-component developer having the color toner, an image forming apparatus having the color toner, and an image formation using the color toner. A method and a method for producing the color toner are provided.

Still another object of the present invention is to use a color toner which hardly causes filming on the surface of the photoreceptor, a two-component developer having the color toner, an image forming apparatus having the color toner, and the color toner. An image forming method and a method for producing the color toner are provided.

Furthermore, an object of the present invention is to provide a color toner having a good dispersibility of a colorant, a two-component developer having the color toner, an image forming apparatus having the color toner,
An object of the present invention is to provide an image forming method using the color toner and a manufacturing method of the color toner.

Further, an object of the present invention is to provide a color toner having a high coloring power and a high image density, a two-component developer having the color toner, an image forming apparatus having the color toner, and the color toner. An object of the present invention is to provide an image forming method used and a method for producing the color toner.

Still another object of the present invention is to use a color toner having high saturation and excellent transparency, a two-component developer having the color toner, an image forming apparatus having the color toner, and the color toner. An image forming method and a method for producing the color toner are provided.

[0039]

The present invention includes at least a coloring agent and the following formula (1).

[0040]

Embedded image A color toner comprising color toner particles containing a non-linear polyester resin synthesized by using a compound represented by: or a acid anhydride thereof, wherein the colorant is formed of pigment particles. The pigment particles in the particles have a number average particle diameter of 0.7 μm or less,
Containing 60% by number or more of pigment particles having a particle diameter of 0.5 μm,
The present invention relates to a color toner containing 10% by number or less of pigment particles having a particle diameter of 0.8 μm or more, and having a softening point temperature Tm of 85 ° C. to 120 ° C. calculated from a flow tester curve. .

The present invention also relates to a two-component developer containing the above color toner and carrier.

Further, the present invention is an image forming apparatus having a latent image carrier for holding an electrostatic charge image and a developing device for developing an electrostatic charge image on the latent image carrier, wherein the developing device is (I) a developer container containing a non-magnetic one-component developer, (ii) a developer carrier for carrying the non-magnetic one-component developer contained in the developer container, and (iii) ) A developer coating member for coating the non-magnetic one-component developer in a thin layer on the developer carrier,
The non-magnetic one-component developer has the above-mentioned color toner, and relates to an image forming apparatus.

Further, according to the present invention, at least one of cyan toner, magenta toner and yellow toner is formed on the recording material.
In the color image forming method, the method comprises the steps of forming a color toner image by using color toners of different colors, and the step of heating and fixing the formed color toner image on a recording material to obtain a color image, wherein the cyan toner, magenta toner, and In the yellow toner, the colorant is a cyan color pigment particle,
The present invention relates to a color image forming method, which is characterized in that the color toner is magenta pigment particles and yellow pigment particles.

Furthermore, the present invention provides a first binder resin having a non-linear polyester resin synthesized by using a compound represented by the above formula (1) or an acid anhydride thereof, a dispersion medium and the dispersion medium. And heating the paste pigment containing 5 to 50% by mass of insoluble pigment particles while mixing under non-pressurized pressure; the pigment particles in the paste pigment are distributed to the heated first binder resin. Or a step of transferring; a step of melt-kneading the first binder resin and the pigment particles to obtain a first kneaded material; a step of drying the obtained first kneaded material; a dried first kneaded material And a step of melt-kneading a mixture having at least a second binder resin to obtain a second kneaded material; and a step of obtaining a color toner particle by cooling the obtained second kneaded material and pulverizing the second kneaded material. And the resulting color toner The pigment particles in the particles have a number average particle diameter of 0.7 μm or less, contain 60% by number or more of pigment particles having a particle diameter of 0.1 to 0.5 μm, and have a particle diameter of 0.8 μm or more. The present invention relates to a method for producing a color toner, which contains 10% by number or less of particles and has a softening point temperature Tm of 85 ° C. to 120 ° C. calculated from a flow tester curve.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION
When the color reproducibility, the highlight reproducibility, the charging stability, the cleaning property, the transfer property, and the like were diligently examined, it was found that the binder resin was the following formula (1).

[0046]

[Chemical 9] When having a non-linear polyester resin synthesized by using the compound shown by or its acid anhydride, and the pigment particles forming the colorant exhibit a specific excellent dispersed particle size as described below. For the first time, they have found that a color toner having high color reproducibility can be provided without adversely affecting offset resistance.

That is, the binder resin according to the present invention has a polyester resin having a weak cross-linking structure, and it is preferable that the diol component and the dicarboxylic acid component are regular in the linear polymer chain. It is a polyester having a weak crosslinked structure in which a trivalent or higher polyvalent carboxylic acid component is introduced as a crosslinkable monomer component. However, even though it has a weak cross-linking structure, the entire polymer is constituted as one three-dimensional polymer, which is more than a simple mixture of linear polymers.
Offset resistance is much improved. The level of cross-linking of the binder resin is within the range that does not hinder the easy mobility of the binder resin due to heat, and by limiting the composition and amount of the monomer components, full color with good color mixing and color reproducibility is obtained. It became possible to obtain an image. However, after all, a slight difference in color reproducibility was inevitably produced when compared with a normal linear polymer having a sharp melt property.

Therefore, in the present invention, a colorant is highly dispersed in order to enhance color reproducibility and color mixing property, that is, the pigment particles in the color toner particles have a number average particle diameter of 0.7 μm.
Pigment particles containing 60 number% or more of pigment particles having a particle size of 0.1 to 0.5 μm and having a particle diameter of 0.8 μm or more, and 10 number% or less of pigment particles having a particle size of 0.8 μm or more. By controlling the dispersed particle size of, it was possible to achieve both improved offset resistance, color reproducibility, and color mixture.

The inventors of the present invention can superimpose toners composed of the binder resin only when the pigment particles in the toner are uniformly dispersed and the dispersed particle size is controlled as described above. Enables reproduction of all color tones,
It has been found that an ideal subtractive color mixing method can realize color tones in various density regions.

That is, when the number average particle diameter of the pigment particles in the color toner particles is larger than 0.7 μm, it basically means that there are many pigment particles which are not sufficiently dispersed. If the color reproducibility and the transparency of the transparency film are not good, and further, if the pigment particles in the toner are present as an agglomerate in a non-uniform state, variations in charging between the toner particles become remarkable, and so-called The tribo distribution will be broad. With this, the desired high-quality full-color image cannot be obtained.

Further, the present invention is also characterized in that the pigment particles in the color toner contain 60% by number or more of pigment particles having a particle diameter of 0.1 to 0.5 μm.

That is, until now, when the dispersed particle diameter of the colorant was discussed, only the average particle diameter was inevitably emphasized. However, according to the study by the present inventors, the colorant is dispersed in the color toner particles. The inventors have found that the dispersed particle size distribution of pigment particles is extremely important for improving color reproducibility.

More specifically, when the dispersed particle size of the pigment particles is broad, there is inevitably a large difference in the degree of dispersion of the colorant between the toner particles. Even if it is made small, diffuse reflection of light due to relatively large colorant particles that are not sufficiently dispersed cannot be avoided, and the desired color reproduction cannot be achieved. In particular, in the subtractive color mixing method by superimposing three colors of magenta, cyan, and yellow, it is desirable that the dispersed particle size distribution be as sharp as possible so that the spectral reflection characteristics of the colorant can be maximized.

Basically, pigment particles having a fine particle size of less than 0.1 μm are considered not to have an adverse effect on the light reflection and absorption characteristics, and provide good color reproducibility and excellent transparency of the transparency film. To do. On the other hand, if there are many pigment particles having a particle size larger than 0.5 μm, the brightness and color of the projected image will inevitably decrease.

Therefore, in the present invention, 0.1 to 0.5
60% by number or more of pigment particles having a particle diameter of μm, preferably 6
The content is preferably 5% by number or more, and more preferably 70% by number or more.

Further, the present invention is characterized by containing 10% by number or less of pigment particles having a particle size of 0.8 μm or more, and basically, it is preferable that the number of particles of 0.8 μm or more is small. When the pigment particles having a large particle diameter of 0.8 μm or more are contained in an amount of more than 10% by number, especially when many pigment particles having such a large particle diameter exist in the vicinity of the surface, the toner surface is inevitable. Is inevitable,
It causes various problems such as fog, drum contamination, and poor cleaning. Furthermore, when such a color toner is used as a two-component developer, it causes a problem such as carrier contamination, and a stable image cannot be obtained in long-term durability. Naturally, good color reproducibility cannot be expected, and uniform chargeability cannot be obtained.

Next, a method of dispersing pigment particles for achieving the object of the present invention will be described.

In the color toner of the present invention, the conventional method of kneading at a high temperature or under pressure as in the prior art easily breaks the molecular chain, improves the offset resistance and improves the image quality of a full-color image. That is, the intended effect in designing the color toner cannot be fully exerted.

In the present invention, in order to achieve the specific dispersion state of the pigment particles in the color toner particles as described above, the first binder resin and the dispersion medium and the pigment particles 5 insoluble in the dispersion medium are used. A paste pigment containing 50% by mass is charged into a kneader or a mixer and heated while mixing under non-pressurization to melt the first binder resin, and the paste pigment, that is, the pigment in the liquid phase is heated. The first binder resin, that is, the molten resin phase, is melted and kneaded with the first binder resin, that is, the molten resin phase, and then the first binder resin and the pigment particles are melted and kneaded. And first with pigment particles
Then, the mixture obtained by adding the second binder resin and, if necessary, additives such as a charge control agent to the first kneaded product is melt-kneaded by heating to obtain the second kneaded product. It is preferable that the obtained second kneaded product is cooled and then pulverized into a toner.

In the present invention, the above-mentioned paste refers to a state in which the pigment particles are present in the pigment particle manufacturing process without any drying process. In other words, the pigment particles are in the state of almost primary particles and are 5 to 5 with respect to the total paste.
It is a state in which 0 mass% is present. The remaining 50 to 95% by mass of the paste is mostly volatile liquid together with some dispersants, auxiliaries and the like. The volatile liquid is not particularly limited as long as it is a liquid that is vaporized by general heating, but the liquid which is particularly preferably used in the present invention and which is preferably used ecologically is water.

In the present invention, the insoluble pigment particles are
The pigment particles are insoluble in the dispersion medium, which is a volatile liquid in the paste, and can be dispersed in the paste. For example, when water is selected as the volatile liquid, all water-insoluble pigment particles are insoluble pigment particles.

The paste pigment used in the present invention contains water-insoluble pigment particles in an amount of 5 to 50% by mass, more preferably 5 to 50% by mass.
It is preferable to contain 45% by mass. When the content of the insoluble pigment exceeds 50% by mass, the dispersion efficiency in the resin is low, the kneading temperature must be high, or the kneading time must be set long. Furthermore, a strong screw or paddle structure is indispensable for the kneading device, which easily causes polymer chain scission.

On the contrary, when the paste pigment contains less than 5% by mass of insoluble pigment in solid content, in order to obtain the intended pigment content, a large amount of paste pigment has to be put into the apparatus. The size of the device cannot be avoided. Further, if it is less than 5% by mass, the process of removing water in the process after the first kneading should be strengthened to completely remove water, resulting in a large load on the resin. Become.

When the paste pigment and the resin are kneaded or mixed, the ratio of the pigment and the resin in terms of solid content is 10:
90-50: 50, preferably 15: 85-45: 55
Is good.

When the ratio of the pigment to the resin is less than 10% by mass, a large amount of the resin has to be charged into the kneading machine with respect to the paste pigment, and segregation of the pigment is likely to occur in the kneaded product, so that this can be made into a uniform system. In order to bring it with you, you have to set a long kneading time. This imposes an extra load on the resin, making it impossible to obtain the desired resin characteristics.

When the ratio of the pigment to the resin is more than 50% by mass, the transfer of the pigment particles in the liquid phase to the resin is not carried out smoothly, and in addition, the kneading is carried out at the time of the melt kneading after the transfer of the pigment particles. The product does not show a uniform molten state, and as a result, high dispersibility cannot be obtained.

As a specific means for achieving the specific dispersion state of the pigment particles of the color toner particles as described above, the first kneaded product and the mixture containing at least the second binder resin are melt-kneaded to obtain the second mixture. When a kneaded product is obtained, a specific non-linear polyester resin as the first binder resin is metal-crosslinked by using an organometallic complex, and the second kneaded product is kneaded in a state in which sufficient shear is applied. Preferably, the kneading conditions of the kneader without using the organometallic complex are, for example, by setting the kneader, lowering the kneading temperature, and the like.
It is also possible to carry out the kneading in a state where the second kneaded product has a sufficient share. However, the former method is more preferable in order to reduce the diameter of the pigment particles and further uniformly disperse the pigment particles so that even the dispersed particle diameter of the pigment can be obtained sharply.

Further, as a means for attaining the specific dispersion state of the pigment particles in the color toner particles as described above, instead of the method using the above-mentioned paste pigment, dry powder-like pigment particles are used as the first means. In the step of melting the binder resin and the pigment particles to obtain the first kneaded product, in order to carry out the kneading more sufficiently than in the past, the number of times of the kneading is more than once, preferably 5 times or more, preferably Can be repeated 8 times or more.

However, when the dispersibility of the pigment particles is improved by increasing the number of times of kneading, mechanical stress is applied to the first binder resin. Therefore, the molecular chain in the first binder resin is broken. And the storage stability of the toner is deteriorated, and a part of the toner is easily taken to the fixing roller due to the durability of a large number of sheets. Therefore, the above-mentioned method using the paste pigment is more preferable than the above-mentioned method using the dry powdery pigment particles from the viewpoint of the durability of a large number of images.

In the present invention, since the first kneading step is performed under no pressure, the softening point temperature Tm calculated from the flow tester curve of the binder resin is preferably 85 ° C to 115 ° C.

When the softening point temperature Tm of the binder resin is higher than 115 ° C., the resin is not sufficiently melted in the step of dispersing under no pressure as in the present invention, and the paste pigment is changed from the water phase to the molten resin phase. The distribution or transition of the above does not occur smoothly, and the dispersed particle size as described above cannot be reached. Further, although a resin having a Tm higher than 115 ° C. is excellent in offset resistance, it is unavoidable that the fixing set temperature is increased.
Moreover, even if the degree of dispersion of the pigment could be controlled, the surface smoothness in the image area would be significantly reduced,
High color reproducibility cannot be expected.

When the resin has a Tm lower than 85 ° C., the kneading process surely proceeds smoothly, but the toner obtained has weak blocking resistance, and even if it is a polyester having a three-dimensional structure, high offset resistance is desired. It's gone.

In the present invention, the reason for melt kneading under non-pressurization is that the liquid in the paste pigment, such as water, violently attacks the polyester resin under pressure, causing a partial hydrolysis reaction, or the deterioration of the resin. May occur, and this may result in the inability to obtain the effect of using the binder resin having a weakly crosslinked structure. Therefore, in the present invention, it is preferable that the first binder resin and the paste pigment are melt-kneaded under no pressure.

Examples of the kneading device used in the present invention include a heating kneader, a single-screw extruder, a twin-screw extruder, and a kneader, and a heating kneader is particularly preferable.

As described above, the color toner of the present invention uses a binder resin satisfying both offset resistance and full-color high image quality, and while maintaining the characteristics of the binder resin in the color toner manufacturing process, The above-described object can be achieved by efficiently and effectively dispersing the colorant in the binder resin.

The softening point temperature Tm calculated from the flow tester curve of the color toner of the present invention is 85 ° C. ≦ Tm.
Another feature is that ≦ 120 ° C.

When the softening point temperature Tm of the toner is higher than 120 ° C., the anti-offset property is excellent, but the fixing set temperature must be increased, and even if the degree of dispersion of the pigment can be controlled. The surface smoothness in the image area is significantly reduced, and high color reproducibility cannot be expected.

When the Tm of the toner is lower than 85 ° C., the smoothness of the surface of the fixed image is surely high and the vividness is visually perceived, but the offset is likely to occur in the durability. Furthermore, the storage stability is poor, and there is a concern about a new problem such as toner fusion in the developing device. Therefore, the softening point temperature Tm of the color toner is 85 ° C. ≦ Tm ≦ 120 ° C., preferably 90 ° C. ≦ Tm ≦ 115 ° C.

Therefore, in the color toner of the present invention, the softening point temperature Tm of the color toner is 85 ° C. to 120 ° C.
In addition to having a temperature of ℃, by using the above-mentioned specific non-linear polyester resin as the binder resin of the color toner, and by having a good specific dispersion state of the pigment particles in the color toner particles, Since the dispersibility of the pigment particles is better than that of the toner, even if the color toner image is fixed at a fixing temperature lower than the conventional fixing temperature and the gloss value of the fixed color image is set to a low value, it is equal to or better than the conventional one. It has the above good color reproducibility and transparency of the color image fixed on the transparency film.

Pigment particles suitable for the purpose of the present invention include conventionally known chromatic colors and black to white pigments.
Among them, organic pigments having high lipophilicity are particularly preferable.

For example, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Examples include phthalocyanine blue, fast sky blue, and indanthrene blue BC.

Highly light-resistant pigments such as polycondensed azo type, insoluble azo type, quinacridone type, isoindolinone type, perylene type, anthraquinone type and copper phthalocyanine type are preferable.

Particularly preferred magenta pigments are
C. I. Pigment Red 1, 2, 3, 4, 5, 6,
7,8,9,10,11,12,13,14,15,1
6, 17, 18, 19, 21, 22, 23, 30, 3
1, 32, 37, 38, 39, 40, 41, 48, 4
9,50,51,52,53,54,55,57,5
8, 60, 63, 64, 68, 81, 83, 87, 8
8, 89, 90, 112, 114, 122, 123, 1
46,150,163,184,185,202,20
6,207,209,238; C.I. I. Pigment Violet 19; C.I. I. Bat red 1, 2, 10, 1
3,15,23,29,35.

Particularly preferred cyan pigments include
C. I. Pigment Blue 2, 3, 15, 16, 17;
C. I. Bat Blue 6; C.I. I. Acid Blue 45
Alternatively, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton having a structure represented by the following formula (2) can be given.

[0085]

[Chemical 10]

Particularly preferred yellow pigments are C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6,
7, 10, 11, 12, 13, 14, 15, 16, 1
7,23,65,73,74,81,83,93,9
5,97,98,109,117,120,137,1
38,139,147,151,154,167,17
3,180,181,183, C.I. I. Butt yellow 1, 3, and 20 are mentioned.

In the present invention, the pasty pigment obtained from the pigment slurry before the filtration step in the known production step of the above colorant without any drying step is a powder which has been dried once. It is more preferable than the one in which the pigment particles are reconstituted with water to form a paste.

The content of the yellow pigment is OH
The yellow toner that sensitively reflects the transparency of the P film is 12 parts by mass or less, preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the binder resin.

When the amount is 12 parts by mass or more, the reproducibility of green and red, which are mixed colors of yellow, and human skin color as an image is poor.

For the other magenta toner and cyan toner, the content of the magenta pigment or the cyan pigment is 15 parts by mass or less, more preferably 0.1 to 9 parts by mass based on 100 parts by mass of the binder resin. Parts by mass are preferred.

In the present invention, the divalent acid component constituting the polyester resin preferably used is, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and diphenyl-P.P'-dicarboxylic acid. , Naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane-P.
P'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P, P'-dicarboxylic acid can be used, and other acids include maleic acid, fumaric acid, glital acid. , Cyclohexanedicarboxylic acid, succinic acid, malonic acid, adipic acid, mesaconic acid,
Itaconic acid, citraconic acid, sebacic acid, anhydrides of these acids, and lower alkyl esters can be used.

The dihydric alcohol is represented by the following formula (3)

[0093]

[Chemical 11]

(In the formula, R ₁ is an alkylene group having 2 to 5 carbon atoms, X and Y are positive numbers, and 2 ≦ X + Y ≦ 6). For example, polyoxypropylene (2 , 2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxypropylene (13) -2,2
-Bis (4-hydroxyphenyl) propane.

Other dihydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
Diols such as 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol and 1,4-butenediol, 1,4-bis (hydroxymethyl)
Cyclohexane, and bisphenol A and hydrogenated bisphenol A are mentioned.

The non-linear polyester resin according to the present invention is
As described above, the following formula (1)

[0097]

[Chemical 12] It is also characterized in that the compound represented by or an acid anhydride thereof is used as an essential component.

Specific examples of the above compounds include those represented by the following formulas (4) to (8).

[0099]

[Chemical 13] Examples of the above compound include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, tri-n-hexyl 1,2,4-tricarboxylate, 1, Triisobutyl 2,4-benzenetricarboxylate, tri-n-octyl 1,2,4-benzenetricarboxylate and tri-2-ethylhexyl 1,2,4-benzenetricarboxylate can be used. However, it is not limited to this.

In the polyester resin of the present invention, for example, maleic acid, fumaric acid, glutaric acid, succinic acid, malonic acid, having n-dodecenyl group, isododecenyl group, n-dodecyl group, isododecyl group, isooctyl group, succinic acid, malonic acid,
Acids having alkyl or alkenyl substituents such as adipic acid and / or ethylene glycol, 1,3-propylene diol, tetramethylene glycol, 1,4
-Alcohol such as butylene diol and 1,5-pentyl diol may be contained.

The production method for obtaining the polyester resin used in the toner of the present invention is, for example, as follows.

First, a linear condensate is formed, and in the process, the molecular weight is adjusted so as to be 1.5 to 3 times the target acid value and hydroxyl value, and the molecular weight is made more uniform than before. To allow the condensation reaction to proceed slowly and gradually, for example, (i) let the reaction proceed at a lower temperature and for a longer time than before, (i
The reaction is controlled by i) reducing the esterifying agent, (iii) using a less reactive esterifying agent, or (iv) using a combination of these methods. Then, under the conditions, a crosslinking acid component and, if necessary, an esterifying agent are further added to react with each other to form a three-dimensional condensate. When the temperature is further raised, the reaction is slowly and long-timed so that the molecular weight distribution becomes uniform, the crosslinking reaction proceeds, and when the hydroxyl value, acid value or MI value decreases to a target value, the reaction is terminated to obtain a polyester resin.

The color toner of the present invention is not limited to the negative charging property or the positive charging property. In the case of using a negatively chargeable toner, it is preferable to add a charge control agent particularly for the purpose of stabilizing negative charge characteristics. Examples of the negative charge control agent include organic metal complexes such as metal complexes of alkyl-substituted salicylic acid (for example, chromium complex or zinc complex of di-tert-butylsalicylic acid).

In the case of a positively chargeable toner, nigrosine, a triphenylmethane compound, a rhodamine dye, or polyvinyl pyridine can be used as a charge control agent having a positive chargeability. In the case of producing a color toner, 0.1 to 40 mol%, preferably 1 to 30 m as a monomer of aminocarboxylic acid-containing esters such as dimethylaminomethyl methacrylate showing positive charging property.
It is preferable to use a binder resin containing ol% or a colorless or pale color positive charge control agent that does not affect the color tone of the toner.

The addition method is not particularly limited.

The color toner of the present invention is preferably composed of a mixture of color toner particles and an external additive. The external additive may be, for example, a fluidity-improving material for improving fluidity of the toner. Agents. As the fluidity improver, by adding to the colorant-containing resin particles, as long as the fluidity can be increased compared to before addition,
Anything can be used.

Fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder;
Fatty acid metal salts such as zinc stearate, calcium stearate, lead stearate, etc .; metal oxides such as titanium oxide powder, aluminum oxide powder, zinc oxide powder, or powders obtained by hydrophobizing the above metal oxides; and wet process silica. , Silica fine powder such as dry process silica, or
The surface-treated fine silica powder obtained by subjecting those silicas to a surface treatment with a treating agent such as a silane coupling agent, a titanium coupling agent, or silicone oil can be used.

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

When the color toner of the present invention is used as a two-component developer, examples of carriers used include surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths. Metals and their alloys or oxides and magnetic ferrites can be used. There is no particular restriction on the manufacturing method.

A system in which the surface of the carrier is coated with a resin is particularly preferable. As the method, there are known methods such as a method of dissolving or suspending a coating material such as a resin in a dissolving agent and applying it to a carrier and simply coating a powder of the coating material by mixing with a carrier. Either method can be applied.

The material adhered to the surface of the carrier (coating material) varies depending on the toner material, but is, for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin. Resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, fine silica powder, fine alumina powder, metal complex or metal salt of dialkylsalicylic acid may be used alone or in combination.

The treatment of the above-mentioned compound (fixed substance) may be appropriately determined so that the carrier satisfies the above conditions.
Generally, the total amount is 0.1 to 30 mass% with respect to the carrier.
(Preferably 0.5 to 20 mass%) is good.

The average particle size of these carriers is 20 to 100.
μm, preferably 25 to 70 μm, more preferably 25
It is preferable to have a thickness of ˜65 μm.

In a particularly preferred embodiment, Cu-Zn-
A ternary ferrite of Fe, the surface of which is a resin such as a fluororesin and a styrene resin, alone or in combination, such as polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate. A resin, a fluorine-based copolymer, or the like is used alone or in a mixture in a preferable ratio at an appropriate time, and 0.01 to 5% by mass, preferably 0.1 to 1% by mass is preferably coated.

When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 1% by mass to 15% by mass, preferably 2% by mass to 1% by mass as the toner concentration in the developer.
Good results are usually obtained when the amount is 3% by mass. If the toner concentration is less than 1% by mass, the image density will be low,
If it exceeds, the fog and scattering in the machine are increased, and the useful life of the developer tends to be shortened.

When the color toner of the present invention is used as a non-magnetic one-component type developer, the above-mentioned magnetic carrier is not used, but the above-mentioned fluidity improver and the like are appropriately added and used.

Next, an image forming apparatus using the non-magnetic one-component developer having the color toner of the present invention will be described.

The image forming apparatus of the present invention has a latent image holding member for holding an electrostatic charge image and a developing device for developing the electrostatic charge image of the electrostatic holding member. ,
(I) a developer container holding a non-magnetic one-component developer having the color toner of the present invention, (ii) a developer for holding the non-magnetic one-component developer held in the developer container A carrier and (iii) a developer coating member for coating the non-magnetic one-component developer in a thin layer on the developer carrier.

The image forming apparatus of the present invention will be described with reference to the schematic explanatory view of a specific example of the developing apparatus using the non-magnetic one-component developer shown in FIG.

The latent image is formed on the latent image carrier 1 by an electrophotographic process means or an electrostatic recording means (not shown). The developer carrier 2 is composed of a non-magnetic sleeve made of metal such as aluminum or stainless steel. The non-magnetic one-component developer is stored in a hopper 3 as a developer container, and is supplied by a supply roller 4 to a developer carrier 2
Supplied up. The supply roller 4 also removes the developer on the developer carrying member 2 after development. The developer supplied onto the developer carrying member 2 is uniformly and thinly applied by a developer applying blade 5 as a developer applying member which elastically comes into pressure contact with the developer carrying member 2. The contact pressure between the developer coating blade 5 and the developer carrying member 2 is 3 to 250 g / cm, preferably 10 to 10 in terms of linear pressure in the sleeve generatrix direction.
120 g / cm is effective. When the contact pressure is less than 3 g / cm, it becomes difficult to apply the developer uniformly, and the distribution of the charge amount of the developer becomes broad, which easily causes fog and scattering. If the contact pressure exceeds 250 g / cm, a large pressure is applied to the toner particles, so that the toner particles are likely to aggregate or be crushed, which is not preferable. By adjusting the contact pressure to 3 to 250 g / cm, it becomes possible to satisfactorily loosen the agglomeration of the small-sized toner particles, and it is possible to instantly increase the triboelectric charge amount of the developer. As the developer coating blade 5, it is preferable to use a triboelectric charging series material suitable for charging the developer to a desired polarity.

In the present invention, the developer coating blade is
Elastic blades made of rubber such as silicone rubber, urethane rubber, styrene-butadiene rubber are preferred. The use of conductive rubber is preferable because it can prevent the toner from being triboelectrically charged excessively. If necessary, the surface of the blade 5 may be coated. In particular, when used as a negative toner, it is preferable to coat a positively chargeable resin such as polyamide resin.

In a system in which a thin layer of developer is coated on the developer carrying member 2 by the blade 5, the thickness of the developer layer on the developer carrying member 2 is set so as to obtain a sufficient image density. It is preferable that the length is made smaller than the facing gap length between the body 2 and the latent image holding member 1, and an alternating electric field is applied to this gap.
A bias power source 6 shown in FIG. 1 applies an alternating electric field or a developing bias in which a direct current electric field is superimposed on the alternating electric field between the developer carrying member 2 and the latent image holding member 1 to apply a latent image from the developer carrying member 2. Facilitates the movement of the developer on the holding body 1,
A higher quality image can be obtained.

Next, the full-color image forming method of the present invention will be described.

According to the color image forming method of the present invention, a color toner image is formed on a recording material using at least one color toner of cyan toner, magenta toner and yellow toner, and the formed color toner image is recorded on the recording material. In order to obtain a color image by heat-fixing, the cyan toner, the magenta toner and the yellow toner have the constitution of the color toner of the present invention.

The color image forming method of the present invention will be described with reference to FIG.
The full-color image forming apparatus using the color image forming method of the present invention shown in FIG.

The color image forming apparatus shown in FIG. 2 includes a recording material conveying system I provided from the right side of the apparatus main body 101 (upper side of FIG. 2) to a substantially central portion of the apparatus main body, and the outline of the apparatus main body 101. A latent image forming section II provided in the central portion in the vicinity of the transfer drum 115 constituting the recording material conveying system I, and a developing unit arranged in the vicinity of the latent image forming section II. That is, it is roughly classified into a rotary developing device III.

The recording material conveying system I has the following structure. Right wall of the device body 101 (right side of FIG. 2)
An opening portion is formed in the opening, and recording material supply trays 102 and 103 that are detachable are arranged in the opening portion so as to partially project out of the machine. Paper feed rollers 104 and 105 are arranged substantially directly above the trays 102 and 103, and these paper feed rollers 104 and 105 are linked to a transfer drum 115 arranged on the left side and rotatable in the arrow direction. As described above, the paper feed roller 106 and the paper feed guides 107 and 10
8 are provided. In the vicinity of the outer peripheral surface of the transfer drum 115, the contact roller 109, the gripper 110, and the recording material separating charger 11 from the upstream side to the downstream side in the rotation direction.
1. The separation claw 112 is sequentially arranged.

A transfer charger 113 and a recording material separating charger 114 are provided on the inner peripheral side of the transfer drum 115. A transfer sheet (not shown) made of a polymer such as polyvinylidene fluoride is attached to a portion of the transfer drum 115 around which the recording material is wound, and the recording material is electrostatically attached on the transfer sheet. It is attached closely to. On the upper right side of the transfer drum 115, a conveyor belt means 116 is disposed in the vicinity of the separation claw 112, and a color toner image is heated on the recording material at the end (right end) of the conveyor belt means 116 in the recording material conveying direction. Fixing device 118 for fixing
Is provided. Further downstream of the fixing device 118 in the transport direction, it extends outside the apparatus main body 101, and
A discharge tray 117 that is detachable from 01 is provided.

Next, the structure of the latent image forming section II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 119, which is a latent image holding member rotatable in the direction of the arrow in FIG. 2, is arranged with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 115. Above the photosensitive drum 119, in the vicinity of the outer peripheral surface thereof, a charger 120 for removing electricity and a cleaning means 121 from the upstream side to the downstream side in the rotation direction of the photosensitive drum 119.
And a primary charger 123 are sequentially arranged, and an image exposure means 124 such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 119, and an image exposure reflection means 125 such as a mirror. It is arranged.

The structure of the rotary developing device III is as follows. A rotatable housing (hereinafter referred to as "rotating body") 1 at a position facing the outer peripheral surface of the photosensitive drum 119.
26 is provided, and four types of developing devices are mounted in the rotating body 126 at four positions in the circumferential direction.
The electrostatic latent image formed on the outer peripheral surface of is visualized (that is, developed). The above-mentioned four types of developing devices respectively include a yellow developing device 127Y, a magenta developing device 127M, a cyan developing device 127C, and a black developing device 127BK.

The sequence of the entire image forming apparatus having the above configuration will be described by taking the case of the full color mode as an example. When the photosensitive drum 119 described above rotates in the direction of the arrow in FIG. 2, the photosensitive member on the photosensitive drum 119 is charged by the primary charger 123. In the apparatus of FIG. 2, the operating speed of each part (hereinafter referred to as process speed) is 100 mm / sec or more (for example, 130 to 250 mm).
/ Sec). When the photosensitive drum 119 is charged by the primary charger 123, image exposure is performed by the laser light E modulated by the yellow image signal of the original 128, an electrostatic latent image is formed on the photosensitive drum 119, and rotation is performed. By the rotation of the body 126, the electrostatic latent image is developed by the yellow developing device 127Y which is fixed at the developing position in advance, and a yellow toner image is formed.

The paper feed guide 107, the paper feed roller 106,
The recording material conveyed through the paper feed guide 108 is
It is held by the gripper 110 at a predetermined timing,
The contact roller 109 and an electrode facing the contact roller 109 are electrostatically wound around the transfer drum 115. The transfer drum 115 is the photosensitive drum 119.
The yellow toner image formed by the yellow developing device 127Y is rotating in the direction of the arrow in FIG.
The outer peripheral surface of the photosensitive drum 119 and the transfer drum 115.
The image is transferred onto the recording material by the transfer charger 113 at a portion in contact with the outer peripheral surface of. The transfer drum 115 continues to rotate and the next color (magenta in FIG. 1)
Prepare for the transfer.

The photosensitive drum 119 is the above charger 12 for static elimination.
After the charge is removed by 0, the toner is cleaned by the cleaning means 121 using a conventionally known blade method, then charged again by the primary charger 123, and image exposure is performed by the next magenta image signal to form an electrostatic latent image.
The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 119 by imagewise exposure with a magenta image signal, and the magenta developing device 127M is placed at the above-mentioned predetermined developing position so that the predetermined magenta is generated. Develop with toner. Subsequently, the above-described process is performed for cyan and black, respectively, and when the transfer of the four color toner images is completed, the four color developed image formed on the recording material is transferred to the chargers 122 and The charge is removed by 114, the gripping of the recording material by the gripper 110 is released, the recording material is separated from the transfer drum 115 by the separating claw 112, and is sent to the fixing device 118 by the conveyor belt 116. After fixing by heating, a series of full-color print sequences are completed, and a required full-color print image is formed on one surface of the recording material.

In the above description, the full-color image is formed by using the four color toners of the black toner in addition to the cyan toner, the magenta toner, and the yellow toner, but the black image is formed without using the black toner. It is also possible to form a full-color image by using three color toners of cyan toner, magenta toner, and yellow toner.

Further, in the present invention, a cyan toner,
It is also possible to form a color image using two colors during formation of a single color image using one of the magenta toner and the yellow toner.
It is also possible to form a full-color image by combining one or more colors of magenta toner and yellow toner with commercially available black toner.

The measuring method in the present invention will be described below.

(1) Measurement of glass transition temperature Tg In the present invention, measurement is carried out using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by Perkin Elmer Co.).

The measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg.

This was placed in an aluminum pan, and an empty aluminum pan was used as a reference, and the measurement temperature range was 30 ° C to 2 ° C.
The measurement is performed at a temperature rising rate of 10 ° C./min between 00 ° C. and normal temperature and normal humidity.

During this temperature rising process, the endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection point between the line at the midpoint of the baseline and the differential heat curve before and after the endothermic peak appears,
The glass transition temperature Tg in the present invention.

(2) Gloss (Glossiness) Measurement Method Using a VG-10 type gloss meter (manufactured by Nippon Denshoku Co., Ltd.), each solid image used for chromaticity measurement is measured as a sample.

For the measurement, first, 6 V was measured by a constant voltage device.
Set to.

Then, the light projecting angle and the light receiving angle are respectively set to 60.
Set to °.

Using the 0-point adjustment and the standard plate, after the standard setting, the sample image is placed on the sample table, and the white paper is 3 times.
Perform overlay measurement on a sheet and read the value shown in the marking section in%.

(3) Measurement of softening point temperature of resin A flow tester CFT-500 type (manufactured by Shimadzu Corporation) is used. A sample weighs about 1.0 g of a 60 mesh pass product. Using a molding machine, this is pressed for 1 minute with a load of 100 kg / cm ² .

The pressure sample is subjected to flow tester measurement under the following conditions at room temperature and normal humidity (temperature of about 20 to 30 ° C., humidity of 30 to 70% RH) to obtain a temperature-apparent viscosity curve. From the obtained smooth curve, the temperature (= T _1/2 ) when the sample flows out by 50% by volume is obtained, and this is taken as the softening point temperature Tm of the resin.

RATE TEMP 6.0 (° C./min) SET TEMP 50.0 (° C.) MAX TEMP 180.0 (° C.) INTERVAL 3.0 (° C.) PREHEAT 300.0 (seconds) LOAD 20.0 (kg) DIE (Diameter) 1.0 (mm) DIE (Length) 1.0 (mm) PLUNGER 1.0 (cm ² )

(4) Measurement of average particle size of pigment particles in color toner particles Toner is added to a 2.3 M sucrose solution, stirred well, put on a sample holder pin in a small amount, and then put into liquid N _2. Then solidify and immediately set on the sample arm head.

A sample was prepared by cutting with an ultramicrotome FC4E (manufactured by Nissei Sangyo Co., Ltd.) equipped with a cryo device according to a conventional method.

An electron microscope H-8000 (manufactured by Hitachi, Ltd.) was used to make an accelerating voltage of 100 kV, and a photograph was taken. The magnification is arbitrary depending on the sample.

The image information is introduced into an image analyzer (Luzex3) manufactured by Nikole Co. through an interface, and 2
Convert to value image data. Among them, only the pigment particles having a particle diameter of 0.1 μm or more are randomly analyzed, the measurement is repeated until the sampling number exceeds 300, and the number average particle diameter of the pigment particles required in the present invention, And the particle size distribution was determined.

That is, here, only particles larger than 0.1 μm were measured. The particle size referred to in the present invention is a value defined by the diameter obtained by spherically approximating each pigment particle image.

[0154]

The present invention will be described in detail with reference to the following examples.

(Production Example-1 of polyester resin) 2 mol of terephthalic acid, dodecenyl succinic anhydride 1.09mo
1, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3.4 mol, and 0.01 g of dibutyltin oxide were added to a glass-made 2 liter of 4 g.
Put in a two-necked flask, thermometer, stirring bar, condenser,
And, a nitrogen introduction tube was attached and placed in the mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised with stirring, the reaction was carried out at 170 ° C. for 5 hours, then the temperature was raised to 190 ° C., and the reaction was carried out for 4 hours. The hydroxyl value of the resin produced at this point was 59.8.

Then, trimellitic anhydride 0.2mo
1 and 0.08 g of dibutyltin oxide were added, and 190
The mixture was reacted at ℃ for 3 hours, further heated to 200 ℃, reacted for 5 hours and the reaction was completed to obtain polyester resin (1).

The softening point of this polyester resin (1) is 1
It was 04 degreeC and the glass transition temperature was 64 degreeC.

(Production Example-2 of Polyester Resin) 1.9 mol of isophthalic acid and 1.22 mo of octyl succinic acid.
1, polyoxyethylene (2.0) -2,2-bis (4
3.34 mol of -hydroxyphenyl) propane was reacted in a nitrogen atmosphere in the same manner as in Production Example-1 of polyester resin. Then trimellitic anhydride 0.13
mol, dibutyltin oxide 0.09g added, 180 ℃
The reaction was carried out for 5 hours to obtain a polyester resin (2).

The polyester resin (2) had a glass transition temperature of 62 ° C. and a softening point temperature of 106 ° C.

(Production Example-3 of polyester resin) 3.0 mol of terephthalic acid, polyoxypropylene (2.2)
-1,2-bis (4-hydroxyphenyl) propane 1.6 mol, polyoxyethylene (2.0) -2,2
-Bis (4-hydroxyphenyl) propane 1.6mo
0.01 g of 1, dibutyltin oxide was placed in a 2 liter glass four-necked flask and reacted in a nitrogen atmosphere in the same manner as in Production Example-1 for polyester resin. Then, 0.3 mol of tri-n-butyl 1,2,4-benzenetricarboxylate was added, the temperature was raised to 220 ° C., the reaction was carried out for 5 hours, and the reaction was terminated to obtain a polyester resin (3).

The softening point of this polyester resin (3) is 1
The glass transition temperature was 01 ° C and the glass transition temperature was 60 ° C.

(Production Example-4 of Polyester Resin) 2.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2- 2.1 mol of bis (4-hydroxyphenyl) propane, 2 mol of terephthalic acid, 1.6 mol of dodecenylsuccinic acid, 0.4 of trimellitic acid
6 mol was reacted at 250 ° C. for 8 hours using the same device as in Production Example-1 of polyester resin to obtain a polyester resin (4).

The polyester resin (4) had a softening point temperature of 118 ° C. and a glass transition temperature of 61.5 ° C.

(Production Example 5 of polyester resin) 2.0 mol of isophthalic acid, 1.4 mol of fumaric acid, 1.5 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, poly Oxyethylene (2) -2,2-bis (4-hydroxyphenyl)
Propane 1.5 mol, dibutyltin oxide 0.02 g
Was placed in a glass 2-liter four-necked flask, and a polyester resin (5) was obtained in substantially the same manner as in Production Example-1 for polyester resin.

The polyester resin (5) had a glass transition temperature of 51 ° C. and a softening point temperature of 82 ° C.

(Production Example 6 of polyester resin) 1.4 mol of fumaric acid, polyoxypropylene (2.2)-
2,2-bis (4-hydroxyphenyl) propane 1.
A polyester resin (6) was obtained in substantially the same manner as in Production Example-1 for polyester resin, using 4 mol and 0.02 g of dibutyltin oxide.

The polyester resin (6) had a glass transition temperature of 58 ° C. and a softening point temperature of 92 ° C.

(Production Example-7 of Polyester Resin) Except that 0.3 mol of 1,2,5-hexanetricarboxylic acid was used in place of 0.2 mol of trimellitic anhydride in Production Example-1 of polyester resin. Polyester resin (7) was obtained in substantially the same manner as in Polyester resin production example-1.

The polyester resin (7) had a glass transition temperature of 58 ° C. and a softening point temperature of 102 ° C.

Obtained polyester resins (1) to (7)
Table 1 shows the glass transition temperature (Tg) and the softening point temperature (Tm) of the above.

[0171]

[Table 1]

Example 1 First Kneading Step Polyester Resin (1) 70 parts by mass C.I. I. Pigment Blue 15: 3 was produced by a known method, water was removed to some extent from the pigment slurry before the filtration step, and a paste-like pigment having a solid content of 30% by mass (remaining 70% by mass) was obtained without any drying step. % Is water) 100 parts by mass

The above raw materials having the above formulation are first charged into a kneader type mixer, and the temperature is raised without pressure while mixing. When the maximum temperature (which is inevitably determined by the boiling point of the solvent in the paste, in this case about 90 to 100 ° C.), the pigment in the water phase is distributed or transferred to the molten resin phase, and this is confirmed. After that, the mixture is heated and melt-kneaded for another 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer is stopped and hot water is discharged, another 1
The temperature was raised to 30 ° C., and the mixture was heated and melted and kneaded for about 30 minutes to disperse the pigment and distill off water. After this step was completed, the mixture was cooled and the kneaded product was taken out. The water content of this final kneaded product was about 0.5% by mass.

Second Kneading Step The above kneaded product (content of pigment particles: 30% by mass) 16.7 parts by mass Polyester resin (1) 88.3 parts by mass Chromium complex of di-tertiarybutylsalicylic acid (charge control agent) 4 parts by mass

The above formulation was sufficiently premixed with a Henschel mixer, and the temperature was 120 ° C. with a twin-screw extrusion kneader.
Set to 1, melt and knead, cool, and then use a hammer mill to approximately 1
Coarsely pulverized to about 2 mm, and then finely pulverized to a particle size of 40 μm or less by an air jet type fine pulverizer. Further, the obtained finely pulverized product is classified, and selected so that the volume average diameter in the particle size distribution is 8.2 μm to obtain cyan toner particles (classified product) for the purpose of improving fluidity and imparting charging characteristics. The cyan toner (A) was prepared by externally adding 1.0 part by mass of titanium oxide fine powder hydrophobized with a Si compound to 100 parts by mass of cyan toner particles.

With respect to 5.0 parts by mass of this cyan toner (A), styrene-methyl methacrylate (copolymer weight ratio 6
5:35) coated with about 0.35% by mass of Cu-
A Zn-Fe type ferrite carrier was mixed so that the total amount was 100 parts by mass to obtain a two-component type developer. The toner concentration in the two-component developer was 5.0% by mass.

A copying test was conducted by using this two-component developer in a commercially available plain paper color copying machine (color laser copier 550) shown in FIG. At this time, the fixing roller has a thickness of 5
2 mm thick RTV (room temperature vulcanizing type) silicone rubber layer on a 1 mm aluminum cored bar, 50 μm thick fluororubber layer on the outside, and 230 μm thick HTV (high temperature vulcanizing type) silicone on the outside. A pressure roller having a diameter of 60 mm is used, and a pressure roller has an RTV silicone rubber layer having a thickness of 2 mm on an aluminum core having a thickness of 5 mm, a fluorine rubber layer having a thickness of 50 μm on the outer side, and an outer side of this layer. Thickness of 200μ
m HTV silicone rubber layer was used.

In this copy test, an initial image was obtained, but the color tone was vivid with excellent saturation.

Further, even after the endurance of 60,000 sheets, a cyan image faithfully reproducing the fog-free original image was obtained,
It had excellent color reproducibility. Conveyance in the copying machine and detection of developer concentration were also good, and stable image density was obtained. Even when the fixing temperature was set to 160 ° C. and 60,000 sheets were repeatedly copied, offset to the fixing roller did not occur at all. In addition,
The occurrence of offset on the fixing roller was determined by visually observing the surface of the fixing roller after repeated copying.

In order to compare and examine the amount of high temperature offset, a new fixing roller was provided in the fixing device. The drive of the silicone oil impregnated web is stopped, and the area ratio 2
Using 0% of the image as the original, 5,000 copies were repeated. After that, the toner attached to the web, so-called,
In order to quantify the high temperature offset toner, the portion was measured with a Macbeth reflection densitometer, and the density was as low as 0.3.

In this method, if the high temperature offset amount is large,
The reflection density value of the toner-attached web increases and decreases when it is small, so that the high temperature offset is quantified.

The charge amount was measured in each environment of low temperature and low humidity (15 ° C./10% RH) and high temperature and high humidity (32.5 ° C./85% RH). The charge amount ratio was 1.35.

As a method of evaluating a color copied image, there is a method of determining the quality of a color image by measuring the gloss (glossiness) of the image surface. That is, it is determined that the higher the gloss value is, the smoother and glossy color quality the image surface has, and conversely, the lower the gloss value, the more the image surface with dull saturation is blurred. In Example 1, the image density at a contrast potential of 300 V was 1.68 (Macbeth reflection density), and the gloss at that time was 21%. The color image formed on the transparency film is transferred to the overhead projector (O
The transparency of the OHP image projected on HP) was also good.

The offset to the fixing roller, the color reproducibility and the transparency of the OHP image in the above examples were evaluated as follows.

The occurrence of offset on the fixing roller was determined by visually observing the surface of the fixing roller after repeated copying.

The color reproducibility was quantitatively evaluated as follows based on the color difference (ΔE) between the original image and the copied image based on the definition of the color system standardized by the International Commission on Illumination (CIE) in 1976. The evaluation was made based on the following evaluation criteria.

ΔE = {(L ₁ ^* -L ₂ ^* ) ² + (a ₁ ^* -a ₂ ^* ) ² + (b ₁ ^* -b ₂ ^* ) ² } ^1/2 [L ₁ ^* : of original image Lightness a ₁ ^* , b ₁ ^* : Hue and saturation indicating the hue and saturation of the original image L ₂ ^* : Lightness a ₂ ^* , b ₂ ^{* of the} copied image: Hue and saturation indicating the hue and saturation of the copied image]

(Evaluation Criteria) A: Excellent color reproducibility and high saturation. ΔE ≦ 5 (good) Δ: A little lacking in vividness, but practically no problem.
5 <ΔE ≦ 10 (possible) ×: Lack of vividness and poor color reproducibility of secondary colors. ΔE
> 10 (No)

The transparency of the OHP image was evaluated based on the following evaluation criteria by projecting a color image formed on a transparency film using a commercially available overhead projector.

(Evaluation Criteria) A: Excellent transparency, no uneven brightness and excellent color reproducibility. (Good) Δ: There is slight uneven brightness, but there is no problem in practical use.
(Fair) ×: uneven brightness and poor color reproducibility. (No)

(Example 2) Magenta toner (B) was obtained in the same manner as in Example 1 except that the following formulation was changed.

First kneading step Polyester resin (2) 58.3 parts by mass C.I. I. Pigment Red 122 25 mass% water paste pigment 100 mass parts Second kneading step Kneaded product from first kneading step (pigment particle content 30 mass%) 16.7 mass parts Polyester resin (1) 88 .3 parts by mass Chromium complex 4 parts by mass

Using the obtained magenta toner (B),
When a durability test by repeated copying was conducted in the same manner as in Example 1, there was no offset to the fixing roller up to 30,000 sheets, and the transparency of the OHP image was excellent.

The maximum image density (Dmax) at this time is 1.
It was 74.

Example 3 A yellow toner (C) was obtained in the same manner as in Example 1 except that the formulation was changed as follows.

First kneading step Polyester resin (3) 80 parts by mass C.I. I. Pigment Yellow 17 20 mass% water paste pigment 100 mass parts Second kneading step Kneaded product from first kneading step (pigment particle content 20 mass%) 17.5 mass parts Polyester resin (3) 86 Parts by mass Chromium complex 4 parts by mass

Using the obtained yellow toner (C),
When a durability test by repeated copying was conducted in the same manner as in Example 1, up to 30,000 sheets, there was no offset to the fixing roller, and the transparency of the OHP image was excellent.

(Embodiment 4) The three color toners of the cyan toner (A) used in Embodiment 1, the magenta toner (B) used in Embodiment 2 and the yellow toner (C) used in Embodiment 3 are used. A full color image was obtained.

As a result, a good image which faithfully reproduces the original image was obtained. 1000 in durability test
Up to 0 sheets, there was no offset to the fixing roller, high image quality was maintained, and full-color images with excellent gradation were obtained for a long period of time. The light transmittance of the OHP image was also very good.

The color reproducibility in the green, blue and red parts was also good.

Example 5 A black toner (X) was obtained in the same manner as in Example 1 except that the following formulation was changed.

First Kneading Step Polyester Resin (1) 70 parts by mass Water paste pigment containing 26% by mass of carbon black having a primary particle diameter of 60 nm 100 parts by mass Second kneading step Kneaded product by the first kneading step 16. 67 parts by mass (carbon black content 27% by mass) Polyester resin (1) 87.83 parts by mass

Obtained Black Toner (X), Example 1
A full-color image was obtained using the cyan toner (A) used in Example 1, the magenta toner (B) used in Example 2, and the yellow toner (C) used in Example 3.

As a result, a good image that faithfully reproduces the original image was obtained. 2000 even in the durability test
Up to 0 sheets, there was no offset to the fixing roller, high image quality was maintained, and full-color images with excellent gradation were obtained for a long period of time. The light transmittance of the OHP image was also good.

Example 6 First Kneading Step Polyester Resin (1) 100 parts by mass Copper phthalocyanine pigment / C. I. Pigment Blue 15: 3 (dry powder) 30 parts by mass

The above materials were sufficiently premixed with a Henschel mixer, melt-kneaded with a three-roll mill 6 times, cooled, and the kneaded product was taken out.

Second Kneading Step Kneaded product (content of pigment particles: 30% by mass) 16.7 parts by mass Polyester resin (1) 88.3 parts by mass Chromium complex (charge control agent) 4 parts by mass

Using the above formulation, a cyan toner (G) having a volume average diameter of 8.1 μm was obtained in the same manner as in Example 1.

Using the obtained cyan toner (G), a durability test by repeated copying was conducted in the same manner as in Example 1, but no offset was observed up to 10,000 sheets, but it was used in Example 3. Using a combination of the yellow toner (C) and the cyan toner (G), images of green were formed in two colors, and the saturation of the green was found in Example 4.
Although it was lower than the saturation of the green in, it was within the practical level for the time being.

(Example 7) In Example 1, except that the chromium compound was not used in the second kneading step, and the temperature of the twin-screw extrusion kneader was set to 100 ° C. and melt kneading was performed. A cyan toner (Y) was obtained in the same manner as in Example 1.

Using the obtained cyan toner (Y), a durability test by repeating copying was conducted in the same manner as in Example 1, and no offset to the fixing roller was observed up to 10,000 sheets. However, the fog increased with the endurance, and only an image with a light overall feeling was obtained. When a green image was formed with two colors using a combination of the yellow toner (C) used in Example 3 and the cyan toner (Y), the green saturation was the same as that of Example 4. It was lower than However, everything was within the practical level.

(Comparative Example 1) Example 2 is the same as Example 1 except that the polyester resin (4) is used in place of the polyester resin (1) used in the first kneading step and the second kneading step. A cyan toner (D) was obtained in the same manner as in 1.

Using the obtained cyan toner (D), a durability test by repeated copying was carried out in the same manner as in Example 1, but no offset to the fixing roller was observed even after 10,000 sheets, but an OHP image was obtained from the initial stage. The light transmittance was unacceptable.

(Comparative Example 2) Example 2 is the same as Example 1 except that the polyester resin (5) is used in place of the polyester resin (1) used in the first kneading step and the second kneading step. A cyan toner (E) was obtained in the same manner as in 1.

Using the obtained cyan toner (E), a durability test by repeating copying was conducted in the same manner as in Example 1. As a result, offset to the fixing roller occurred at an unacceptable level from the initial stage of durability.

(Comparative Example 3) 100 parts by mass of polyester resin (1) Copper phthalocyanine pigment / C.I. I. Pigment Blue 15: 3 (dry powder) 5 parts by mass Chromium complex (charge control agent) 4 parts by mass

The above formulation was sufficiently premixed with a Henschel mixer, the temperature was set to 120 ° C. with a twin-screw extrusion kneader, and the mixture was melt-kneaded. Then, the same procedure as in Example 1 was performed to obtain a cyan toner having a volume average diameter of 8.0 μm. (F) was obtained.

Using the obtained cyan toner (F), a durability test by repeated copying was conducted in the same manner as in Example 1. As a result, an image with a lot of fog was obtained from the initial stage, and toner scattering was also confirmed. At a durability of 10,000 sheets, some offset was observed on the roller surface.

Using the yellow toner used in Example 3 and this cyan toner (F) in combination, images of two colors of green were produced. The saturation of green was the same as that of green in Example 4. It has decreased significantly compared to the degree. That is, the cyan toner (F) could not achieve good color reproduction.

(Comparative Example 4) Example 2 is the same as Example 1 except that the polyester resin (6) is used in place of the polyester resin (1) used in the first kneading step and the second kneading step. A cyan toner (H) was used in the same manner as in Example 1 to perform a durability test by repeating copying in the same manner as in Example 1. As a result, an offset was observed on the roller surface after 10,000 sheets, and the durability was interrupted.

(Comparative Example 5) Example 5 is the same as Example 1 except that the polyester resin (7) is used in place of the polyester resin (1) used in the first kneading step and the second kneading step. A cyan toner (I) was obtained in the same manner as in 1.

Using the obtained cyan toner (I), a durability test by repeated copying was conducted in the same manner as in Example 1. As a result, the offset resistance was good, but the transparency of the OHP image was poor from the beginning, and the saturation was reduced. Was also low.

Comparative Example 6 A cyan toner (J) was prepared in the same manner as in Example 6 except that the number of kneading in the first kneading step was changed from 6 to 2. Obtained.

Using the obtained cyan toner (J), a durability test by repeating copying was conducted in the same manner as in Example 1. As a result, the transparency of the OHP image was poor from the initial stage, and the yellow toner (C) and this cyan toner ( When the images of green were formed in two colors by using J.), the saturation of green was lower than that in Example 6 and was at an unusable level.

(Comparative Example 7) In Example 6, the polyester resin (6) was used in place of the polyester resin (1) used in the first kneading step and the second kneading step, and the first kneading step was used. A cyan toner (K) was obtained in the same manner as in Example 6 except that the number of times of kneading was changed from 6 to 2.

Using the obtained cyan toner (K), a durability test by repeating copying was conducted in the same manner as in Example 1. As a result, offset was observed on the roller surface after 5000 sheets and the durability was interrupted.

(Comparative Example 8) The same as Example 1 except that the polyester resin in the first kneading step was heated and mixed with the pasty pigment at 120 ° C. under pressure. To obtain a cyan toner (L).

Using the obtained cyan toner (L), a durability test by repeated copying was carried out in the same manner as in Example 1. As a result, a slight offset was observed on the surface of the fixing roller after 10,000 sheets. The softening point of Toner (L) had dropped to 101 ° C., and it is considered that the molecular chains were broken by heating and mixing under pressure.

(Comparative Example 9) In Example 1, the polyester resin (6) was used in place of the polyester resin (1) used in the first kneading step and the second kneading step, and further in the first kneading step. A cyan toner (M) was obtained in the same manner as in Example 1 except that the polyester resin and the paste pigment were heated and mixed at 120 ° C. under pressure.

A durability test by repeated copying was conducted in the same manner as in Example 1 using the obtained cyan toner (M). As a result, an image with a lot of fog was obtained from the initial stage, and toner scattering was also confirmed. A slight offset was observed on the roller surface at a durability of 5000 sheets.

Comparative Example 10 A cyan toner (N) was obtained in the same manner as in Example 1 except that the chromium di-tertiarybutylsalicylate complex used in the second kneading step was not used. Got

Using the obtained cyan toner (N), a durability test by repeated copying was conducted in the same manner as in Example 1. As a result, an image with a lot of fog was obtained from the initial stage, and toner scattering was also confirmed. Also, the transparency of the OHP image was lower than that in Example 1.

Physical properties of Toners A to N, X and Y used in the above Examples and Comparative Examples are shown in Table 2, and evaluation results of Examples 1 to 7 and Comparative Examples 1 to 10 are shown in Table 3.

[0234]

[Table 2]

[0235]

[Table 3]

(Embodiment 8) A cyan toner (A) similar to that of Embodiment 1 except that the developing device in the color electrophotographic apparatus is replaced with a developing device using a non-magnetic one-component type developer as shown in FIG. ) Was used to repeatedly copy 5.0 thousand sheets under high temperature and high humidity, but there was no fusion to the developing sleeve 2, the blade 5 and the supply roller 4, and the image density was as high as 1.70 at a potential contrast of 300V. Dmax was obtained.

[0237] Scattering in the machine and fog due to the decrease in the charge amount of the toner did not occur. During that time, no offset to the fixing roller occurred.

The evaluation results are shown in Table 4.

Example 9 The procedure of Example 8 was repeated, except that the cyan toner (A) was replaced by the magenta toner (B) used in Example 2. The durability test was performed by copying.

Table 4 shows the evaluation results.

(Example 10) The procedure of Example 8 was repeated, except that the yellow toner (C) used in Example 3 was used in place of the cyan toner (A). The durability test was performed by copying.

Table 4 shows the evaluation results.

Example 11 The same procedure as in Example 8 was repeated except that the cyan toner (G) used in Example 6 was used in place of the cyan toner (A) in Example 8. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Example 12) The procedure of Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced with the cyan toner (Y) used in Example 7. The durability test was performed by copying.

Table 4 shows the evaluation results.

(Comparative Example 11) The same procedure as in Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced with the cyan toner (D) used in Comparative Example 1. The durability test was performed by copying.

Table 4 shows the evaluation results.

Comparative Example 12 The procedure of Example 8 was repeated except that the cyan toner (A) used in Comparative Example 2 was replaced with the cyan toner (E) used in Comparative Example 2. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 13) The procedure of Example 8 was repeated, except that the cyan toner (A) in Example 8 was replaced with the cyan toner (F) used in Comparative Example 3. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 14) The procedure of Example 8 was repeated except that the cyan toner (H) used in Comparative Example 4 was used in place of the cyan toner (A) in Example 8. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 15) The procedure of Example 8 was repeated except that the cyan toner (A) used in Example 8 was replaced by the cyan toner (I) used in Comparative Example 5. The durability test was performed by copying.

Table 4 shows the evaluation results.

Comparative Example 16 The procedure of Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced with the cyan toner (J) used in Comparative Example 6. The durability test was performed by copying.

Table 4 shows the evaluation results.

Comparative Example 17 The procedure of Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced by the cyan toner (K) used in Comparative Example 7. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 18) The same procedure as in Example 8 was repeated except that the cyan toner (A) used in Example 8 was replaced with the cyan toner (L) used in Comparative Example 8. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 19) The procedure of Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced by the cyan toner (M) used in Comparative Example 9. The durability test was performed by copying.

The evaluation results are shown in Table 4.

(Comparative Example 20) The procedure of Example 8 was repeated except that the cyan toner (A) in Example 8 was replaced with the cyan toner (N) used in Comparative Example 10. The durability test was performed by copying.

The evaluation results are shown in Table 4.

[0267]

[Table 4]

[0268]

INDUSTRIAL APPLICABILITY In the present invention, a colorant having the above-mentioned non-linear polyester resin as a binder resin is used, and a coloring agent having a specific particle size distribution is added to the binder resin. Since it is dispersed, it is possible to form a color image having excellent fixing properties, color mixing properties, triboelectric charging properties, and glossiness, and having high image density, high saturation, and excellent transparency.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing a specific example of a developing device using a non-magnetic one-component toner to which the color toner of the present invention can be applied.

FIG. 2 is a schematic explanatory diagram of a full-color image forming apparatus using the color image forming method of the present invention.

[Explanation of symbols]

 1 latent image carrier (photosensitive drum) 2 developer carrier (developing sleeve) 3 hopper 4 supply roller 5 developer coating blade 6 power supply

Claims (28)

[Claims] 1. At least a colorant and the following formula (1): A color toner having color toner particles containing a non-linear polyester resin synthesized by using a compound represented by: or a acid anhydride thereof, wherein the colorant is formed of pigment particles. The pigment particles in the particles have a number average particle diameter of 0.7 μm or less, contain 60% by number or more of pigment particles having a particle diameter of 0.1 to 0.5 μm, and have a particle diameter of 0.8 μm or more. A color toner containing 10% by number or less of particles, and having a softening point temperature Tm of 85 to 120 ° C. calculated from a flow tester curve. 2. The non-linear polyester resin according to claim 1, wherein the linear polymer chain has a crosslinked structure in which the linear polymer chain is crosslinked with the compound represented by the formula (1) or an acid anhydride thereof. The described color toner. 3. The non-linear polyester resin is one synthesized by reacting a linear polyester with a compound represented by the formula (1) or an acid anhydride thereof. The color toner described in 1. 4. The color toner according to claim 1, wherein the color toner particles contain an organometallic compound. 5. The color toner according to claim 4, wherein the organometallic compound is an organometallic complex. 6. The color toner according to claim 1, wherein the color toner contains a mixture of the color toner particles and an external additive. 7. The color toner according to claim 6, wherein the external additive contains a fluidity improver. 8. The fluidity improver is a fluorine-based resin powder,
The color toner according to claim 7, which has one or more members selected from the group consisting of fatty acid metal salts, metal oxides, and silica fine powder. 9. A two-component developer having a color toner having color toner particles and a carrier, wherein the color toner particles include at least a colorant and a compound represented by the following formula (1): Containing a non-linear polyester resin synthesized by using a compound represented by or an acid anhydride thereof, the colorant is formed of pigment particles, the pigment particles in the color toner particles, It has a number average particle size of 0.7 μm or less, contains 60 number% or more of pigment particles with a particle size of 0.1 to 0.5 μm, and contains 10 number% or less of pigment particles with a particle size of 0.8 μm or more. The color toner has a softening point temperature Tm of 85 to 120 ° C. calculated from a flow tester curve, which is a two-component developer. 10. The two-component developer according to claim 9, wherein the color toner is the color toner according to any one of claims 2 to 8. 11. An image forming apparatus having a latent image holding member for holding an electrostatic charge image and a developing device for developing the electrostatic charge image on the latent image holding member, wherein the developing device comprises (i) A developer container containing a non-magnetic one-component developer, (ii) a developer carrier for carrying the non-magnetic one-component developer contained in the developer container,
And (iii) a developer coating member for coating the non-magnetic one-component developer in a thin layer on the developer carrier, wherein the non-magnetic one-component developer is a colorant and the following formula. (1) [Chemical Formula 3] A color toner having color toner particles containing a non-linear polyester resin synthesized by using a compound represented by the following formula or an acid anhydride thereof, wherein the colorant is formed of pigment particles, The pigment particles in the color toner particles have a number average particle diameter of 0.7 μm or less, contain 60% by number or more of pigment particles having a particle diameter of 0.1 to 0.5 μm, and have a particle diameter of 0.8 μm or more. 10% by number or less of the pigment particles, and the color toner has a softening point temperature Tm of 85 ° C. to 120 ° C. calculated from a flow tester curve. 12. The image forming apparatus according to claim 11, wherein the latent image holding member is an electrophotographic photosensitive member. 13. The developer applying member elastically presses against the developer carrying member.
2. The image forming apparatus according to item 2. 14. The developer coating member is a rubber blade formed of one or more materials selected from the group consisting of silicone rubber, urethane rubber, and styrene-butadiene rubber.
The image forming apparatus according to any one of 1 to 13. 15. The thickness of the developer layer applied on the developer carrying member is thinner than the facing gap length between the latent image holding member and the developer carrying member. 15. The image forming apparatus according to any one of 14. 16. The image forming apparatus according to claim 11, wherein the color toner is the color toner according to any one of claims 2 to 8. 17. A step of forming a color toner image on a recording material by using at least one color toner of cyan toner, magenta toner and yellow toner, and heating and fixing the formed color toner image on the recording material. In a color image forming method having a step of obtaining a color image, a) the cyan toner contains at least a colorant and the following formula (1): Cyan toner particles containing a non-linear polyester resin synthesized by using a compound represented by the formula (1) or an acid anhydride thereof, wherein the colorant is formed of cyan pigment particles. The cyan pigment particles in the toner particles have a number average particle diameter of 0.7 μm or less and 0.1 to 0.5 μm.
60% by number or more of the cyan color pigment particles having a particle size of 0.8 μm or more,
The cyan toner has a softening point temperature Tm of 85 ° C. to 120 ° C. calculated from a flow tester curve, and b) the magenta toner contains at least a colorant and the following formula (1): ) [Chemical 5] And a magenta toner particle containing a non-linear polyester resin synthesized by using a compound represented by The magenta pigment particles in the toner particles are
The number average particle size is 0.7 μm or less, 0.1 to 0.5
The magenta toner contains 60 number% or more of the magenta pigment particles having a particle size of 0.8 μm, and 10 number% or less of the magenta pigment particles having a particle size of 0.8 μm or more. It has a softening point temperature Tm of 85 ° C. to 120 ° C. calculated from a curve, and c) the yellow toner contains at least a coloring agent and the following formula (1): And a yellow toner particle containing a non-linear polyester resin synthesized by using a compound represented by the formula (1) or an acid anhydride thereof, wherein the colorant is formed of yellow pigment particles. The yellow pigment particles in the toner particles are
The number average particle size is 0.7 μm or less, 0.1 to 0.5
The yellow toner contains 60% by number or more of the yellow pigment particles having a particle size of μm, and 10% by number or less of the yellow pigment particles having a particle size of 0.8 μm or more. A color image forming method having a softening point temperature Tm of 85 to 120 ° C. calculated from a curve. 18. The color image is a full color image formed by combining the cyan toner, the magenta toner and the yellow toner.
The image forming method described in 1 .. 19. The image forming method according to claim 17, wherein the color image is a full-color image formed by combining a black toner in addition to the cyan toner, the magenta toner, and the yellow toner. . 20. The cyan toner, the magenta toner, and the yellow toner are all the color toners according to any one of claims 2 to 8.
20. The image forming method according to any one of 19 to 19. 21. The following formula (1): A first binder resin having a non-linear polyester resin synthesized using a compound represented by: or an acid anhydride thereof,
Dispersion medium and pigment particles insoluble in the dispersion medium 5 to 50
Heating while mixing with a paste pigment containing mass% under non-pressurization; distributing or transferring the pigment particles in the paste pigment to the heated first binder resin;
A step of melt-kneading the first binder resin and the pigment particles to obtain a first kneaded product; a step of drying the obtained first kneaded product; a dried first kneaded product and a second binder A method for producing a color toner, comprising the steps of melt-kneading a mixture having at least a resin to obtain a second kneaded product; and cooling the obtained second kneaded product and pulverizing to obtain color toner particles. The pigment particles in the obtained color toner particles have a number average particle diameter of 0.7 μm or less, contain 60% by number or more of pigment particles having a particle diameter of 0.1 to 0.5 μm, and have a particle diameter of 0.8 μm. A method for producing a color toner, comprising 10% by number or less of pigment particles having the above particle diameter, and the color toner having a softening point temperature Tm of 85 to 120 ° C. calculated from a flow tester curve. 22. The method for producing a color toner according to claim 21, wherein the dispersion medium contains water. 23. The method for producing a color toner according to claim 21, wherein the paste pigment contains 5 to 45% by mass of pigment particles. 24. The mixing ratio between the pigment particles and the first binder resin is in the range of 10:90 to 50:50, and the mixing ratio is preferably in the range of 10:90 to 50:50. Color toner manufacturing method. 25. The second kneaded material is obtained by melt-kneading the dried first kneaded material, the mixture of the second binder resin and the organometallic complex. 25. The method for producing a color toner according to any one of claims 21 to 24. 26. The first kneaded product is obtained by repeating melt-kneading of the first binder resin and the pigment particles five times or more. 5. The method for producing a color toner according to any one of 1. 27. The first kneaded material is obtained by repeating melt-kneading of the first binder resin and the pigment particles eight times or more. 5. The method for producing a color toner according to any one of 1. 28. The first binder resin is 85 ° C. to 115 ° C.
28. The method for producing a color toner according to claim 21, wherein the method has a softening point temperature of.