JP3191072B2 - Full-color toner and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry developer in electrophotography, and more particularly to a two-component developing method using a non-magnetic toner and a carrier and a full-color copying machine using a one-component developing method using a magnetic toner. The present invention relates to an image forming method and a full-color toner capable of suitably embodying the image forming method.

[0002]

2. Description of the Related Art In recent years, the development from white-black copying machines to full-color copying machines has been rapidly progressing, and two-color copying machines and digitized full-color copying machines have begun to be sold in the market.

In general, color image formation by full-color electrophotography uses three color toners of three primary colors, yellow, magenta, and cyan, or reproduces colors using four colors including black.

According to the general method, first, an electrostatic latent image is formed on a photoconductive layer by passing light from a document through a color separation light transmitting filter having a complementary color relationship with the color of the toner. Then development,
After the transfer step, the toner is held on the support. Next, the above-described steps are sequentially performed a plurality of times, and while the registration is being performed, the toner is superimposed on the same support, and the final full-color image is obtained by performing the fixing only once.

Generally, in such an electrophotographic method,
Many developing methods are known, and among these developing methods, a magnetic brush method, a cascade method, and the like using a two-component developer mainly composed of a toner and a carrier have been widely put to practical use. Each of these methods is an excellent method for obtaining a good image relatively stably, but has the common drawbacks associated with the two-component developer, such as deterioration of the carrier and fluctuation of the mixing ratio of the toner and the carrier.

In order to avoid such drawbacks, various developing methods using a one-component developer consisting of toner alone have been proposed, but many of them are excellent in methods using a developer consisting of magnetic toner particles. .

[0007] Among the materials used for magnetic toners, particularly, magnetic substances are often contained in an amount of 20 to 70% by weight based on the whole toner, and this is a factor which greatly affects the performance of the toner. For example, as shown in JP-A-58-189646, a magnetic toner containing a magnetic powder having an FeO content of 16 to 25% by weight can surely obtain a high electrostatic image development efficiency and a good transfer efficiency. However, since the copying machine has been moving toward higher speeds in recent years, the above-mentioned magnetic toner containing a magnetic powder having an FeO content of 16 to 25% by weight has high resolution and high durability. The properties cannot be sufficiently satisfied. Further, when a full-color image or the like is obtained by a multi-color developing method, it is difficult to control the delicate color tone of black, which causes a hindrance to clear colors.

On the other hand, in recent years, new user needs in the market accompanying the widespread use of full-color copying machines have been demanding full-color copying machines, printers, and the like to have functions of both monochrome and black-and-white machines. In other words, in an office environment,
There is a demand for a copying machine capable of obtaining a clear, high-quality full-color image while maintaining the same speed and stable quality as that of a general black-and-white machine. In such a case, the frequency of use of the black toner alone increases and the toner consumption inevitably increases. Therefore, the black toner in a general-purpose full-color copying machine that will be required in the future has excellent image quality and durability stability. Things are desired.

When an image is formed by combining a plurality of developers having different surface properties such as a magnetic toner and a non-magnetic toner, magnetic toner particles comprising a magnetic material and a binder resin, a colorant, a binder, At present, it is difficult to always stably maintain the pressure-bonded state between the photoconductor and the cleaning blade because the non-magnetic toner particles made of resin have different slipping properties or scraping properties from the photoconductor.

In using a magnetic toner and a non-magnetic toner together in the development process of such a full-color copying machine,
The problems caused by the differences as described above must be solved. That is, in the magnetic toner, the dispersion state of the magnetic powder in the binder resin is regarded as a problem, while in the non-magnetic toner, the dispersion of the color dye and the pigment in the binder resin and the improvement of the light transmittance are problematic. In addition, after solving such a problem, the fact that both toners finally have excellent fixability can be cited as an indispensable factor in such a case.

Furthermore, in order to obtain a fixed full-color image, irregular reflection due to toner particles is suppressed as much as possible, and appropriate gloss and gloss are required, and the toner layer of a different color tone under the toner layer is not hindered. It must be a color toner having transparency and wide color reproducibility.

As color toners that can satisfy these requirements,
The present applicants disclose Japanese Patent Application Laid-Open No. 50-82442,
JP-A-1-144625 and JP-A-59-57256 have disclosed a novel combination of a color binder resin 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 close to complete melting at the time of fixing, which is preferable. Gloss and color reproducibility can be obtained.

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

That is, at the time of heating, the toner behaves more viscously, the thermal melting property increases, and the gloss is obtained.

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

In particular, when a silicone rubber roller is used as a fixing roller, a high-temperature offset is likely to occur due to a substantial decrease in the releasability of the surface of the silicone rubber roller which is repeatedly used regardless of whether a releasing oil is applied. At the beginning of use of silicone rubber rollers,
Due to the smoothness and cleanliness of the roller surface, some releasability can be maintained. However, the image area is large like a color image, and the toner holding amount on a support such as plain paper is also
If color copying, which is much more common than white and black copying images, is continued to be copied, the releasability of the roller gradually decreases. The speed at which the releasability deteriorates reaches several times that of black and white copying.

Further, since the toner itself has almost no elasticity as described above, it is ineffective for the anti-offset effect. As a result, after only several thousand to several tens of thousands of sheets, a toner film or a granular attachment is formed on the surface of the fixing roller, and the toner upper layer on the image surface is peeled off when passing through the heat roller. A so-called high-temperature offset occurs.

Various approaches have been tried with toner 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, JP-A-58-60144
As described in, for example, JP-A-123852, a method of adding a low-molecular-weight polyethylene, polypropylene, wax, higher fatty acid, or the like, which is a releasing component, to a toner in order to increase releasability is also performed. Although these methods are effective in preventing offset, they contain a large amount that is sufficiently effective in offset resistance, resulting in poor compatibility with the main binder resin and impairing the transparency of color toner OHP images. In addition, adverse effects such as unstable charging characteristics and reduced durability are also observed, and it is difficult to say that these are sufficient.

Further, Japanese Patent Application Laid-Open Nos. 47-12334, 57-37353, and 57-20855
In JP-A-9, a monomer containing an etherified bisphenol monomer, a dicarboxylic acid monomer, a trihydric or higher polyhydric alcohol monomer and / or a trivalent or higher polyhydric carboxylic acid monomer is disclosed. A toner containing, as a binder, a polyester made of a non-linear copolymer obtained from a component has been proposed, but such a technique involves a polyester made of an etherified bisphenol monomer and a dicarboxylic acid monomer, Offset to the toner by incorporating a polyester obtained by crosslinking with a large amount of a monomer component containing a trihydric or higher polyhydric alcohol monomer and / or a trivalent or higher polyhydric carboxylic acid monomer as a binder. It has a preventive performance. However, in such a toner, its softening point is slightly high, so that good low-temperature fixing is difficult, and when used for full-color copying, high-temperature offset resistance is at a level that can be practically used. As described above, since the fixing property and the sharp melt property are difficult, the color mixing property and the color reproducibility due to the superposition of the full-color toner using the polyester cannot be expected. JP-A-57-109825, JP-A-62-78568, JP-A-62-78569, and further JP-A-59-7960 and JP-A-5-79569.
JP-A-9-29256 discloses an etherified bisphenol monomer, a dicarboxylic acid monomer or other dicarboxylic acid monomer into which a long-chain aliphatic hydrocarbon is introduced, and a trihydric or higher polyhydric alcohol monomer. And / or a non-linear copolymer obtained from a monomer component containing a trivalent or higher polycarboxylic acid monomer, wherein the side chain has a saturated or unsaturated fatty acid having 3 to 22 carbon atoms. Discloses a toner containing a polyester having an aromatic hydrocarbon group as a binder,
These polyester resins are mainly intended for toners for high-speed copying.The viscoelastic properties of the resin are, as opposed to the viscosity-oriented polyester described above, completely enhanced elasticity and markedly offset high-temperature offset to the rollers. It has been reduced. At the time of fixing, the pressure and heating of the heat roller are increased as much as possible, and the toner is pressed into the semi-molten state between the fibers of the transfer paper, and the pressure and heat are fixed to achieve the object. is there.

Therefore, it is almost impossible to obtain a smooth surface by fusing the toner layer necessary for color copying to form a continuous film, and the fixed toner exists in the form of particles on the transfer paper. The image is dull and poor in saturation, and in the OHP image, light is scattered and diffused on the surface of the toner particles, hardly transmits light, and becomes practically unusable.

Further, Japanese Patent Application Laid-Open Nos. 2-73366 and 1-2224776 disclose a novel polyester resin having excellent hot offset resistance and applicable to color copying. I see.
Although it is superior to the conventional color toner resin, the effect of preventing the offset to the fixing roller is exhibited at most about 20,000 to 50,000 repeated copies, and the effect of preventing the black and white toner from offset is more than 100,000 sheets. In view of printing durability and offset resistance of several hundred thousand sheets at present, it is preferable to further improve the performance. The polyester has been studied with the primary problem of fixability in color copying. In terms of charging, the difference in charge between a low-temperature, low-humidity environment and a high-temperature, high-humidity environment is large. , The density tends to be slightly lower on the low humidity side, and toner scattering or fogging may occur on the high humidity side.

Also, Japanese Patent Application Laid-Open No. Sho 62-195676,
JP-A-62-195678, JP-A-62-195
Japanese Patent Publication No. 680 discloses a polyester resin in which the ratio between the hydroxyl value and the acid value is specified. However, these polyester resins are also intended for high-speed fixing, and are examined by the present inventors. The color toner using the resin did not reach the point where sufficient color mixing was obtained.

Particularly, a problem peculiar to color copying is at least 3
The color balance of the color toners, preferably four, must be balanced, and it is meaningless to discuss the fixing characteristics and color reproducibility of only one color.

In principle, if there are three primary colors of yellow, magenta, and cyan, almost all colors can be reproduced by the primary color mixing method.
Therefore, currently available full-color copying machines have a configuration in which three primary color toners are superposed. This should ideally enable all colors to be achieved in all density ranges, but in reality, there are still points that need to be improved, such as the spectral reflection characteristics of the toner, the mixing properties when superimposing and fixing the toner, and the decrease in chroma. have.

In the case where black is obtained by superimposing three colors, three times more toner layers are formed on the transfer paper than in the case of a single color, and furthermore, it is necessary to further reduce the offset resistance.

Various other methods have been proposed for improving the binder resin.

For example, Japanese Patent Application Laid-Open No. Sho 56-158340 proposes a toner comprising a low molecular weight polymer and a high molecular weight polymer, but it is difficult for this binder resin to actually contain a crosslinking component. Therefore, in order to improve the offset resistance with higher performance, it is necessary to increase the molecular weight or increase the ratio of the high molecular weight polymer. This direction is a direction in which pulverizability is remarkably reduced, and it is difficult to obtain a practically satisfactory one. Further, with respect to a toner blended with a low molecular weight polymer and a cross-linked polymer,
JP-A-86558 proposes a toner containing a low molecular weight polymer and an insoluble and infusible high molecular weight polymer as main resin components. According to the method, the fixability and the pulverizability are thought to be improved, but the insoluble infusible high molecular weight polymer is 40 to 40%.
When it is as large as 90 wt%, it is difficult to satisfy the high performance with the offset resistance and the pulverization property. In practice, unless the fixing machine has a device for supplying the liquid for preventing offset, the fixing property, the anti-offset property, It is extremely difficult to produce a toner that satisfies pulverizability sufficiently. Furthermore, if the amount of the insoluble infusible high molecular weight polymer is increased, the melt viscosity becomes very high in the hot kneading at the time of toner preparation, so that the heat kneading is performed at a much higher temperature than usual, or the heat kneading is performed at a high share As a result, as a result, the former has a problem that the toner characteristics are deteriorated due to the thermal decomposition of other additives, and the latter has a problem that excessive cutting of the molecules of the binder resin occurs and the initial anti-offset performance is hardly obtained. Further, when a magnetic powder or a dye or pigment is contained in the binder resin, a good dispersion state cannot be obtained.

[0029] Furthermore, in JP-A-56-16144, in molecular weight distribution by GPC, the molecular weight 10 ³ to
There has been proposed a toner containing a binder resin component having at least one having a maximum value in each region of 8 × 10 ⁴ and a molecular weight of 10 ⁵ to 2 × 10 ⁶ . In this case, pulverizability, offset resistance, fixing property, filming and fusing to a photoreceptor, image properties, and the like are excellent, but further improvement in offset resistance and fixing property of the toner is demanded.
In particular, it is difficult for a material such as the binder resin to meet today's strict requirements while further improving the fixing property and maintaining or improving various other performances.

A binder resin which solves such a problem is disclosed in Japanese Patent Application Laid-Open No. Sho 63-223014. However, at present, even higher durability and higher reliability are required. It is becoming impossible to respond.

Further, the binder resin has a large effect on the developability, and a binder resin having a particularly stable triboelectric charge is desired for toner.

On the other hand, various devices have been developed for the fixing step based on such a background. At present, the most common method is a pressure heating method using a heat roller.

In the pressure heating method using a heating roller, the toner is fixed by allowing the toner image surface of the sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having releasability while applying pressure. In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and It can fix, and is very effective in high-speed electrophotographic copying machines and the like.

However, as described above, in an electrophotographic process in which a magnetic toner and a non-magnetic toner are developed in multiple layers to obtain a visible image, the fixing properties of the toner layers are affected by the various properties of each toner layer. At present, it is difficult to sufficiently pull out only by the fixing process.

Further, in such a system in which the magnetic toner and the non-magnetic toner are mixed and multiplexed on the same image, there is a problem that the fixed images of the magnetic toner and the non-magnetic toner have different surface smoothness. 20 to 50 magnetic powder in magnetic toner
It is mixed at a ratio of 70% by weight, and the apparently uniform image surface is in a rough state after fixing, whereas the non-magnetic toner containing a dye and pigment is completely melted, The surface smoothness is better than that. Because of this, the reflection angle of the light that shows the luster of human eyes is different, and the nonmagnetic toner has high gloss, whereas the magnetic toner has poor gloss. In the case where the image is obtained, there arises a problem that the texture of the obtained image changes.

[0036]

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

That is, an object of the present invention is to provide a full-color toner having stable color reproducibility, high image density and high durability in a full-color toner using three color toners and a black toner, and image formation using the toner. To provide a method, in full-color copying, it shows good fixing and color mixing properties, has sufficient triboelectricity, has a high gloss that greatly enhances image quality, and is less likely to cause carrier spent even after repeated copying. An object of the present invention is to provide a color toner which has excellent durability, sufficiently prevents high-temperature offset, has a wide fixing temperature range, and maintains offset resistance even after repeated fixing.

[0038]

The full-color toner of the present invention is a full-color toner for forming a color image by appropriately using at least one of yellow toner, magenta toner and cyan toner together with a black toner. The yellow toner, magenta toner and cyan toner are non-magnetic toners in which an external additive is externally added to colored resin particles in which a colorant is mixed and dispersed in a binder resin, and the black toner is F in magnetic iron oxide
A magnetic toner in which an external additive is externally added to magnetic resin particles in which a black magnetic powder and a release agent having an eO content in a range of 25 to 30% by weight are mixed and dispersed in a binder resin,
The binder resins used for the yellow toner, magenta toner and cyan toner include the following components (a), (b) and (c).
And (d) (a) 25 to 35 mol% of the total monomer amount of a divalent aromatic acid component (a) selected from isophthalic acid, terephthalic acid and derivatives thereof, and (b) trimellitic acid and derivatives thereof. The selected trivalent aromatic acid component (b) is used in an amount of 2 to 4 mol based on the total amount of monomers.
%, (C) a divalent acid component (c) selected at least from dodecenyl succinic acid, octyl succinic acid and its anhydride, 12 to 18 mol% of the total monomer amount, (d) propoxylation and / or ethoxylation. The etherified diphenol component (d) is used in an amount of 45 to 6 based on the total amount of the monomers.
A polyester resin produced from a monomer composition containing at least 0 mol%, wherein the polyester resin has a hydroxyl value of 10 to 20 and a weight average molecular weight of 13,000 to 2
0000 and a number average molecular weight of 5,000 to 8,000.
0, weight average molecular weight (Mw) / number average molecular weight (M
n) is 2 to 3.5, and the binder resin used in the black toner contains at least the following components (e) and (f): (e) a dicarboxylic acid monoester monomer, and (f) divinylbenzene. The divinylbenzene was added to the dicarboxylic acid monoester monomer in an amount of 0.0
A styrene-acrylic copolymer resin produced from a monomer composition containing 1 to 5% by weight;
The acid value of the acrylic copolymer resin is 2 to 100 mgKOH
/ G, the acid value derived from the acid anhydride of the resin is 10 mgK
OH / g or less, and in the molecular weight distribution measured by GPC of the resin component, a region having a molecular weight of 5,000 or less is 15%
, Having a main peak in the region of molecular weight 5000 to 100,000, and having a weight average molecular weight of 5,000,000
It is characterized by being at least 00.

Further, according to the image forming method of the present invention, at least one of the above-mentioned yellow toner, magenta toner and cyan toner is appropriately and selectively used together with the above-mentioned black toner to form an electrostatic latent image on an electrostatic image carrier. The image is developed to form a toner image, and the toner image is sequentially transferred onto a transfer material to form an image.

As described above, the full-color toner of the present invention
An optimal binder resin is used for each of a non-magnetic color toner (a yellow toner, a magenta toner, and a cyan toner) and a magnetic black toner. Hereinafter, the color toner and the black toner will be described in detail. .

<Color Toner> It can be said that the polyester resin according to the present invention has the characteristics of both a linear polyester resin and a non-linear crosslinked polyester resin, that is, has a transient nature. Thus, it is considered that good color mixing properties and color reproducibility as a color toner were obtained, and that offset resistance to the fixing roller was obtained.

That is, the reason why preferable characteristics are obtained in the present invention is presumed as follows.

(I) Trimellitic acid, which is a cross-linking monomer component, contains 20 to 30 units of a condensate of one molecule of a divalent acid component and one molecule of a dihydric alcohol component in a linear condensate chain repeated. At most one molecule is introduced to form weak crosslinks. And although it is a weak crosslink, the entire condensate in the polyester is constituted as one three-dimensional polymer. This provides much better offset resistance than a mixture of mere linear polyesters. However, the level of cross-linking of the present invention is also within a range that does not prevent easy mobility of the polyester resin by heat.

(Ii) By extremely limiting the composition and amount of the divalent acid component having a soft segment,
A full-color image with good color mixing and color reproducibility can be obtained, and
The offset resistance is not adversely affected. In the weakly crosslinked condensate in the feature (i), the amount of the cross-linking acid component and the amount of the acid component are determined so as to be naturally balanced, and if too large, an abnormal sharp melt property is generated,
On the other hand, if the amount is too small, the gloss and the saturation of the color image are reduced.

In the present invention, while using a trivalent carboxylic acid as an essential component, the molecular weight distribution is narrower than that of an ordinary crosslinked binder resin (Mw / Mn = 2 to 3.5, preferably 2.0 to 3). .0), the above effect can be achieved.

(Iii) The other divalent acid component is isophthalic acid or terephthalic acid, and a composition having elasticity without decreasing the viscosity of the polymer is selected as much as possible. On the other hand, when the fatty acid component is changed, the molecular chain becomes linear and long, so that the molecular chain is easily moved by heat, and the polymer exhibits more viscous behavior, so that the fixing roller Offset to is easier.

(Iv) The production conditions of the polyester resin of the present invention are changed from those of the prior art, and the molecular weight distribution of the resin is changed as much as possible.
Special adjustments are made to give a sharp and narrow distribution. It is important to make the distribution of the molecular chains of the condensate in the polyester uniform within a narrow range in order to achieve both the color mixing property and the offset resistance in the color toner. That is, a condensate with a short molecular chain having a small molecular weight is easily heated, and the main chain of the molecule moves. Conversely, a condensate with a long molecular chain having a high molecular weight hardly moves with its thermal energy. When the unbalance is present in the polyester resin, when the color toner using the resin passes through a low-temperature fixing roller, the low-molecular condensate quickly melts and exhibits a behavior of fixing and mixing colors, In addition, a phenomenon occurs in which the polymer condensate hardly dissolves.

On the other hand, if a high temperature at which the polymer is melted is applied to the fixing roller, the low molecule behaves as a viscous material having no elasticity at all, and causes a high temperature offset.

Therefore, especially in the case of a color toner, the ratio between the weight average molecular weight and the number average molecular weight must be relatively high in order to have relatively sharp meltability and to increase the intermolecular aggregation of the polyester resin constituting the toner. Needs to be as small as possible. This is an important attribute beyond that discussed for black and white toner.

(V) In the feature (iv), it has been stated that changing the production conditions of the polyester resin is indispensable for controlling the molecular weight distribution, but it is also necessary to keep the hydroxyl value within a certain range. This manufacturing condition is necessary. The hydroxyl value is a measure of the hydratability of the resin and is an important factor influencing the chargeability of the color toner. If the value is too large or too small, favorable charging characteristics cannot be obtained.

The value of the hydroxyl value is determined only by the production conditions of the composition constituting the polyester resin of the present invention. However, in order to achieve both the fixing property and the charging property satisfying the color mixing property, the color reproducibility and the offset resistance of the color toner, the conditions (i) to (v) must be satisfied.

Although the monomer composition and the like of the present invention can be seen at first glance to be similar to the prior art, the true aim of the present invention and the attained technical achievement cannot be attained with the conventional polyester resin and color toner. It is a thing.

Therefore, in the present invention, the monomer component,
It is extremely difficult to achieve the object of the present invention when the composition ratio and various physical properties are in ranges other than those disclosed by the present invention.

The preferred etherified diphenol in the present invention is an etherified bisphenol. Preferred etherified bisphenols are ethoxylated or propoxylated, having 2-3 moles of oxyethylene or oxypropylene per mole of bisphenol.

As a method for producing the polyester resin of the present invention, for example, the following method is used.

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 higher than before so that the molecular weight becomes uniform. In order for the condensation reaction to proceed slowly and slowly, for example, the reaction is carried out at a lower temperature and longer time than before, or the esterifying agent is reduced, or an esterifying agent having low reactivity is used, or a combination of these methods is used. , Etc. to control the reaction. Thereafter, under these conditions, a crosslinking acid component and, if necessary, an esterifying agent are further added, and the mixture is reacted to form a three-dimensional condensate. The temperature rises further,
The reaction is allowed to proceed slowly and for a long time so that the molecular weight distribution becomes uniform, the crosslinking reaction is advanced, and the reaction is terminated when the hydroxyl value decreases to a target value to obtain the polyester resin of the present invention. For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl)
Propane.

The following pigments or dyes may be mentioned as colorants for color toners suitable for the purpose of the present invention. still,
In the present invention, C.I. I. Disperse
Y164; I. Solvent Y77 and C.I.
I. Colorants such as Solvent Y93 are not recommended.

As the dye, for example, C.I. I. Direct red 1; I. Direct red 4; I. Acid Red 1; I. Basic Red 1; I.
Modant Red 30; I. Direct blue 1;
C. I. Direct blue 2; I. Acid Blue 9; I. Acid blue 15; I. Basic blue 3; I. Basic blue 5; I. Modant Blue 7 and the like.

As the pigment, 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, phthalocyanine blue, fast sky blue, indanthrene blue BC and the like.

Preferably, disazo yellow, insoluble azo pigments, copper phthalocyanine are used as pigments, and basic dyes and oil-soluble dyes are suitable as dyes.

Particularly preferably, C.I. I. Pigment Yellow 17; I. Pigment Yellow 15; I. Pigment Yellow 13; I. Pigment Yellow 1
4; I. Pigment Yellow 12; I. Pigment Red 5; I. Pigment Red 3; I.
Pigment Red 2; I. Pigment Red 6;
C. I. Pigment Red 7; I. Pigment Blue 15; I. Pigment Blue 16 or a copper phthalocyanine pigment having the structural formula (I) shown below and having a phthalocyanine skeleton substituted with two or three substituents.

[0062]

Embedded image As the dye, C.I. I. Solvent Red 49;
I. Solvent Red 52; I. Solvent Red 109; I. Basic Red 12; I. Basic Red 1; I. Basic Red 3b and the like.

The content of the yellow toner which is sensitive to the transmittance of the OHP film is as follows.
12 parts by weight or less based on 100 parts by weight of the binder resin,
Preferably, it is 0.5 to 7 parts by weight.

When the content is 12 parts by weight or more, the reproducibility of human skin color is inferior as a mixed color of yellow, green and red, and an image.

For other magenta and cyan color toners, the amount is preferably 15 parts by weight or less, more preferably 0.1 to 9 parts by weight, based on 100 parts by weight of the binder resin.

The color toner according to the present invention preferably contains a charge control agent in order to stabilize the negative charge characteristics. At that time, a colorless or light-colored negative charge control agent which does not affect the color tone of the toner is preferable.

It is desirable to use a carrier in combination with the color toner of the present invention. Examples of the carrier include metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths whose surface is oxidized or not oxidized. 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 immersed in a resin or the like is particularly preferable. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a dissolving agent, coating and attaching to a carrier, or a method of simply mixing with a powder can be applied.

The substance adhered to the carrier surface varies depending on the toner material. Examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, Polyvinyl butyral, nigrosine, amino acrylate resin,
It is appropriate to use one or a plurality of basic dyes and lakes thereof, fine silica powder, fine alumina powder, metal complexes or metal salts of dialkylsalicylic acid, and the like.

The treatment of the above compound may be appropriately determined so that the carrier satisfies the above conditions, but is generally 0.1 to 30% by weight (preferably 0.5 to 30% by weight) based on the carrier of the present invention. -20% by weight).

The average particle size of these carriers is 20 to 100.
μm, preferably 25-70 μm, more preferably 25
It preferably has a thickness of up to 65 μm.

In a particularly preferred embodiment, Cu—Zn—
A ternary ferrite of Fe, which is a coated magnetic ferrite carrier having the above average particle diameter of not less than 70% by weight of carrier particles of 250 mesh pass and 350 mesh on is mentioned.

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectricity to the toner of the present invention, and has the effect of improving electrophotographic properties.

When a two-component developer is prepared by mixing with the color toner according to the present invention, the mixing ratio is 1% by weight to 15% by weight, preferably 2% by weight, as the toner concentration in the developer.
Good results are usually obtained at weight percents of up to 13 weight percent. If the toner concentration is less than 1% by weight, the image density will be low. If the toner concentration is more than 15% by weight, fog and scattering in the machine will increase, and the useful life of the developer tends to be shortened.

<Black Toner> In the black toner of the present invention, the styrene-acryl copolymer resin of the present invention has a molecular weight distribution in which the region having a molecular weight of 5,000 or less is less than 15% (preferably 2 to 14%, more preferably 2 to 14%). Is 3 to 13%), which has improved blocking resistance, prevents fusing to a pulverizer, fusing to a toner carrier and a photoreceptor, and filming, and has good storage stability. It can be. In addition, excessive pulverization can be suppressed, generation of ultrafine powder can be reduced, production efficiency can be increased, and good developability can be achieved.

It is considered that the components having a molecular weight of 5,000 or less tend to have a molecular weight dependence of the glass transition point (Tg), and the toner Tg measured over a long period of time tends to be lower. Therefore, when the amount of these components increases, that is, 15%
However, the thermal behavior below the normally measured Tg is exhibited, and the performance expected from the Tg of the toner cannot be satisfied.

For example, in a high-speed system, frictional heat at the cleaner portion of the photosensitive member is large, so that fusion and filming are likely to occur. Further, when the toner is continuously produced for a long time, fusion may occur inside the pulverizer.

Further, the toner tends to aggregate in the toner container during storage and transportation of the toner. This is due to the condition under pressure (for example, in a large toner container having a capacity of 1 kg or more,
This is because the blocking resistance in a state where the toner itself is weighted and left still) is inferior.

This component is a component that particularly improves the pulverizability of the toner. However, if the content is too large, if it exceeds 15%, pulverization occurs more than necessary, resulting in increased generation of ultrafine powder and deterioration of classification efficiency. It will reduce productivity.

If the toner contains a large amount of ultrafine powder that cannot be further classified, the content gradually increases as toner replenishment is repeated, and the ultrafine powder adheres to the frictional charging member of the toner due to electrostatic force. However, this also hinders the frictional charging of the toner and causes deterioration in developability such as image density reduction and fogging.

The styrene-acrylic copolymer resin used for the black toner of the present invention has a molecular weight of 5,000,000.
The above components are characterized in that they are 5% or more, preferably 7 to 30%. Particularly preferably, 10% to 25%
It is. These components are excellent in releasability, suppress flow at high temperatures, effectively act as components for improving anti-offset properties, and can prevent toner from flowing out of the fixing device cleaning member. The conventional toner has a small amount of these components, and it has not been possible to effectively prevent the toner from flowing out.

That is, if it is less than 5%, the outflow of toner cannot be prevented. On the other hand, if it exceeds 30%, it becomes difficult to deform during melting, which is disadvantageous for fixing, and the amount of a region serving as a main component for fixing is relatively reduced, which is disadvantageous for improvement of fixing property.

As a component that imparts rubber elasticity to the toner, a so-called gel component (a component that cannot pass through an 80-mesh wire net when put into toluene and has a dense network structure or a large molecular weight) However, the component of the present invention has a large network structure compared to the above-mentioned gel component and is small, so that the molecules are in a state of easy movement, and the deformation of the toner Does not overly resist and does not hinder fixing.

The molecular weight is 100,000-5,000,
The component in the 000 region is preferably 35% or less, particularly preferably 10 to 30%.

These components function as components for improving the resistance to offset against high-temperature offset (adhesion of toner to the fixing roller at high temperatures), but cannot prevent toner outflow from the fixing device cleaning member. The effect is small even if it is increased. That is, in order to prevent toner outflow, the above-mentioned component having a molecular weight of 5,000,000 or more is essential, and its effect is great. Therefore, the components in this region are neither components for improving the fixing property nor components for preventing toner outflow, so that it is not necessary to include a large amount of components in other regions in order to increase the components.

However, it acts as a linking component from a medium molecular weight to an ultra-high molecular weight, makes the anti-offset component and the fixing component uniform, assists the respective effects, and improves the dispersion of the internal additive component in the toner. It is also particularly preferable that the content be contained in the range of 10% to 30%. Conventional toners use components in this region to provide offset resistance. Certainly, there was an effect on offset resistance,
It did not work to prevent toner outflow.

The styrene-acrylic copolymer resin is characterized in that the main peak (the highest peak) is in a molecular weight range of 5,000 to 100,000, and especially 10,000 to 50,000. Is preferably in the region of Further, when there are a plurality of peaks, it is also preferable that a large peak (a sub-peak having a height equal to or more than の of the main peak) is in the range of 5,000 to 100,000.

That is, a component of 10,000 or less functions as a component for improving pulverizability, and a component of 5,000 to 10
The components in the region of 0000 are components for improving the fixing property. That is, in order to contain these components in a well-balanced and large amount, the main peak needs to be in the above-mentioned region, and as a result, good crushability and fixability can be obtained. Therefore, since the components in this region are the main components, the components in the 5,000 to 100,000 region are preferably 40% or more, more preferably 45% or more, and the peak in this region is 10,000 to 100%. 40,000
Is also one of the preferred forms.

When the main peak is less than 5,000,
The same problem occurs when the above-mentioned component of 5,000 or less accounts for 15% or more. If it exceeds 100,000, sufficient fixability and pulverizability cannot be obtained. And 5
From around about 000, the crushability starts to decrease gradually.

In the average molecular weight calculated from the GPC chromatogram, the weight average molecular weight (Mw) was 5,0
It is characterized by being at least 00,000, preferably from 6,000,000 to 20,000,000.
When the molecular weight is 5,000,000 or more, the weight fraction from the high molecular weight to the ultrahigh molecular weight is smoothly connected, and the molecular weight is 5,000,000.
The anti-offset component of 000 or more is effectively contained (including a component of 5,000,000 or more widely, that is, a weight fraction around 5,000,000 is not large, but This means that the components are included in a wide distribution, that is, in the GPC chart, the distribution in the vicinity is not a vertical distribution but a horizontal distribution is better.) , The dispersion of the internal additive is improved. 5,000,0
If it is less than 00, the offset resistance may not be sufficiently obtained. On the other hand, when it exceeds 20,000,000, a fixing failure or a dispersion failure may occur. Further, in order to effectively contain the fixing property improving component and the pulverizing property improving component, the number average molecular weight (Mn) is 40,000 or less, preferably 30,000 or less, more preferably 25,000 or less.
000 or less. In order to contain the above two components in a well-balanced manner and to make the actions of both components more effective, the molecular weight distribution is preferably wide, and Mw / Mn is 1
It is more than 25, preferably 170 or more. Further, it preferably contains a wide range of ultrahigh molecular weight components for preventing toner outflow, and has a Z average molecular weight of 20,000.
It is good to be more than 0000. Further, in order to contain the ultrahigh molecular weight components in a well-balanced manner, Mz / Mw is preferably 40 or less, and more preferably 5 to 30. When the ratio exceeds 40, the amount of the ultra-high molecular weight is included, but when the ratio is small, sufficient prevention of toner outflow cannot be performed. Conversely, when cross-linking increases and filtration is performed by a filter, sufficient fixability cannot be obtained. If it is less than 5, the distribution in the soluble component becomes narrower toward the ultrahigh molecular weight side, so that the balance between the prevention of toner outflow and the fixability deteriorates.

The acid value of the polymer measured by a method according to JIS K-0070 is preferably 2 to 100 mgKOH / g, more preferably 5 to 70 mgKOH / g.
H / g. When the acid value is less than 2 mgKOH / g, the recrosslinking reaction is not sufficiently performed. The acid value is 100m
If it exceeds gKOH / g, it is difficult to control the charge, and the environment-dependency of the developability tends to appear.

The acid value derived from the acid anhydride is 10 mgK
OH / g or less, more preferably less than 6 mgKOH / g. Acid value derived from acid anhydride is 10mgKOH
/ G, the re-crosslinking reaction occurs violently, causing excessive crosslinking, hindering the movement of the molecular chain,
It causes deterioration of fixability. Also, it becomes difficult to control the degree of crosslinking. This is because the reactivity of the acid anhydride group is higher than other acid groups.

Further, by having an acid value, the releasability from the fixing roller is increased, and the offset resistance is improved.

When the component having a molecular weight of 5,000,000 or more has an acid value, it has an affinity such as a hydrogen bond with a polar group in the polymer chain, a magnetic substance added to the toner, a pigment, or a polar group in the dye. A weak bond is formed due to the property, and the flow of the toner at a high temperature can be suppressed softly, so that the prevention of toner outflow and the fixing property can be achieved at the same time.

If the acid anhydride is contained in a large amount, the crosslinking proceeds, and it becomes an insoluble component that cannot pass through the filter, so that it is apparently not observed by GPC.

In order to obtain a vinyl polymer having an acid anhydride, an acid anhydride monomer is used, and besides using a known polymerization method, the following method is mentioned as an example. In a solution polymerization method using a monomer such as dicarboxylic acid or dicarboxylic acid monoester, a part of the dicarboxylic acid or dicarboxylic acid monoester unit can be partially dehydrated by devising conditions for distilling off the dicarboxylic acid or dicarboxylic acid monoester unit when distilling off the solvent. Furthermore, the dicarboxylic acid and the dicarboxylic acid monoester can be dehydrated by subjecting the vinyl copolymer obtained by the bulk polymerization method or the solution polymerization method to heat treatment. Further, the anhydride can be partially esterified with an alcohol or the like.

Conversely, the vinyl copolymer thus obtained can be hydrolyzed to open the anhydride to partially form a dicarboxylic acid.

On the other hand, using a dicarboxylic acid monoester monomer, a vinyl copolymer obtained by a suspension polymerization method or an emulsion polymerization method is subjected to a heat treatment, a hydrolysis treatment to dehydrate and a ring-opening to form an anhydride and a dicarboxylic acid. Obtainable. In addition, a method in which a vinyl copolymer obtained by a bulk polymerization method or a solution polymerization method is dissolved in a monomer and a vinyl polymer is obtained by a suspension polymerization method or an emulsion polymerization method is used. The moiety can be opened to give a dicarboxylic acid. At this time, another resin may be mixed in the monomer, and the resulting resin can be subjected to dehydration, ring opening, and esterification by heat treatment, weak alkaline water treatment, and alcohol treatment.

Incidentally, since dicarboxylic acid and dicarboxylic anhydride monomers have strong alternating polymerizability, it is necessary to obtain a dicarboxylic acid monoester in order to obtain a vinyl copolymer in which functional groups such as anhydride and dicarboxylic acid are randomly dispersed. A polymerization method using a monomer is one of the preferable methods.

The formation and annihilation of the anhydride in the polymer can be confirmed since the infrared absorption of the carbonyl shifts to a higher wave number side (1750 to 1850 cm ^-1 ) than that of the acid or ester.

The binder resin polymerized using the dicarboxylic acid monoester monomer performs a uniform crosslinking reaction because carboxyl groups, anhydride groups, dicarboxylic acid groups, and the like are randomly and uniformly dispersed in the binder resin. be able to.

The acid value derived from the acid anhydride is JIS K-0.
As an example, a method of applying acid value measurement of 070, measurement of hydrolysis acid value (measurement of total acid value) and the like can be mentioned.

For example, in the acid value measurement according to JIS K-0070 (hereinafter referred to as JIS acid value), about 50% of the theoretical value of an acid anhydride is measured (the acid anhydride has an acid value as a dicarboxylic acid). Is done.

On the other hand, in the measurement of the total acid value, it is measured almost according to the theoretical value. Therefore, the difference between the total acid value and the JIS acid value is about 50% of the theoretical value, and the acid anhydride is measured as a dibasic acid.
The total acid value derived from the acid anhydride per gram is determined. One-half of the total acid value is J derived from acid anhydride in JIS acid value.
IS acid value.

In the present invention, the total acid value is determined as follows. 2 g of sample resin is dioxane 30
Then, 10 ml of pyridine, 20 mg of dimethylaminopyridine and 3.5 ml of water are added thereto, and the mixture is refluxed for 4 hours while stirring. 1 / 10N KOH ・ T after cooling
The acid value obtained by neutralizing titration with HF solution using phenolphthalein as an indicator is defined as the total acid value.

The preparation of a 1 / 10N KOH.THF solution is performed as follows. 1.5 g of KOH is dissolved in about 3 ml of water, and 200 ml of THF and 30 ml of water are added thereto, followed by stirring. After standing, a small amount of methanol is added if the solution is separated, and a small amount of water is added if the solution is turbid to make a uniform transparent solution, and standardized with a 1 / 10N HCl standard solution.

The resin component of the black toner characteristic of the present invention can be obtained, for example, by the following method.

Applying solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting, etc.
A polymer (A-1) having a main peak in the range of 00 to 20,000 is formed.

Next, the polymer (A-1) was prepared by adding 0.5 to 20 wt% (preferably 1 to 1) of a carboxyl group-containing monomer.
5 wt%), and subjected to a suspension polymerization reaction. The molecular weight distribution of GPC using THF as a solvent was 5,0 to 5,0%.
A polymer (B-1) having a main peak in the range of 100 to 100,000 and optionally containing a gel component is obtained.

The polymer and the metal-containing compound which reacts with the carboxyl group of the polymer are melted and kneaded with a shear, the high cross-linked high molecular weight component in the resin is cut, reacted with the metal-containing compound, and re-cross-linked. Can be obtained.

This method can be carried out at the time of toner production, and may be carried out by melt-kneading with a magnetic substance and a colorant. Further, the re-crosslinking reaction can be effectively performed by the heat generated at the time of cutting the molecular network.

Further, a carboxyl group-containing monomer is added in an amount of 0.5
A suspension polymerization of a polymerizable monomer having a molecular weight distribution of 5,000 to 10 wt% (preferably 1 to 15 wt%) is performed.
It may contain a gel component having a main peak in a region of 0000. A polymer (A) having a main peak in a region of 2,000 to 100,000 obtained by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting, or the like; -2) may be blended and mixed at the time of melt-kneading.

A polymer (B-B) obtained by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like, having a carboxyl group, a carboxyl group derivative group, and having a molecular weight of 100,000 or more as a main component (B- 3) Polymer (A-1) or polymer (A-2) blended in a solvent at the end of solution polymerization may be melt-kneaded.

Further, the polymer (B-3) and the polymer (A-1)
Alternatively, it may be blended and mixed with the polymer (A-2) during melt kneading.

When the main peak of each polymer in the above resin is in the range of 5,000 to 50,000, it is also a preferable embodiment to obtain a polymer such that both peaks overlap. is there.

Further, the polymer (A-1) and the polymer (A-
The inclusion of a carboxyl group or a carboxyl group derivative group in 2) is also a preferred embodiment.

The polymer used in the black toner of the present invention is a vinyl resin, polyester, polyurethane,
A mixture of two or more of epoxy resin, polyamide, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, haloparaffin, paraffin wax and the like may be used. Further, a block copolymer or a grafted product may be used.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. When obtaining low molecular weight in the composition,
preferable.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.
The initiator is di-tertbutyl peroxide, te
rt-butyl peroxybenzoate, benzoyl peroxide, 2,2′-azobisisobutyronitrile,
2,2'-azobis (2,4 dimethylvaleronitrile)
Is used at a concentration of 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) based on 100 parts by weight of the monomer. The reaction temperature varies depending on the solvent used, the initiator, and the polymer to be polymerized, but is preferably from 70 ° C to 230 ° C. In the solution polymerization, it is preferable to perform the polymerization at 30 parts by weight to 400 parts by weight with respect to 100 parts by weight of the solvent.

It is also preferable to mix another polymer in the solution at the end of the polymerization, and several types of polymers can be well mixed.

As a polymerization method for obtaining a high molecular weight component in a highly crosslinked region, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and since the phase in which the polymerization is carried out (the oil phase composed of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is small, and as a result, the polymerization rate is large. , With a high degree of polymerization.
Further, the reason is that the polymerization process is relatively simple, and that the polymerization product is fine particles, so that it is easy to mix with the colorant, the charge control agent, and other additives in the production of the toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. Therefore, suspension polymerization is a simple method.

The magnetic iron oxide having an FeO content of 25 to 30% by weight used in the black toner of the present invention has a high blackness as a black pigment and stabilizes the toner charge amount to maintain an appropriate electric resistance. This has the effect of improving the image density and improving the fog rank on the image in terms of developability.

Here, when a magnetic iron oxide having an FeO content of less than 25% by weight is used for the toner, it becomes difficult to appropriately control the toner charge amount in a low-temperature and low-humidity environment, and the image density due to an excessive increase in the toner charge amount is reduced. It is not possible to sufficiently cope with the deterioration and the stain on the background, and it is also difficult to control a color tone for obtaining a clear color as a black toner.

On the other hand, when a magnetic iron oxide having an FeO content of more than 30% by weight is used for the toner, the charge amount of the toner is reduced particularly in a high humidity environment, and the image density is reduced.

This magnetic material has an average particle of 0.1 to 2 μm,
Preferably about 0.1 to 0.5 μm,
The amount contained in the toner is about 20 to 200 parts by weight, preferably 10 parts by weight, per 100 parts by weight of the resin component.
40 to 150 parts by weight to 0 parts by weight is good.

The magnetic iron oxide used in the present invention is iron sulfate (F
eSO ₄ ) is neutralized with caustic soda (NaOH) and Fe (O
H) ₂ is obtained, the pH is adjusted to 12 to 13 by alkali adjustment, and then oxidized by steam and air to obtain a magnetite slurry. In the next drying step, the drying temperature and the drying time are controlled using a hot air drier, so that the FeO in the magnetic iron oxide is controlled.
Can be controlled. After the drying is completed, the powder is crushed to obtain a magnetite powder.

Here, the measurement of FeO in the magnetic iron oxide is performed according to the following procedure.

Put 1,000 g of magnetic iron oxide in a 500 ml beaker, add 50 ml of deionized water, and further add 20 ml of special grade sulfuric acid to completely dissolve the magnetic iron oxide.

Next, 100 ml of deionized water was added, and Mn was further added.
SO ₄ , H ₂ SO ₄ and H ₃ PO ₄ (molar ratio: 0.3:
2.0: After the MnSO ₄ mixture 10ml was added a total of 180ml consisting 2.0) were taken 10ml, 0.
Titrate with 1N KMnO ₄ solution.

Then, according to the following formula, 1.000 g of magnetic iron oxide was obtained.
The FeO (%) contained therein is determined.

[0133]

(Equation 1) As the fluidity improver used in the present invention, any one can be used as long as it can be added to the colorant-containing resin particles to increase the fluidity before and after the addition. Examples thereof include hydrophobic colloidal silica fine powder, colloidal silica fine powder, hydrophobic titanium oxide fine powder, titanium oxide fine powder, hydrophobic alumina fine powder, alumina fine powder, and a mixed powder thereof.

If necessary, a fatty acid metal salt such as zinc stearate, aluminum stearate or the like, or a fine powder of a fluorine-containing polymer such as polytetrafluoroethylene, polyvinylidene fluoride or the like and tetrafluoroethylene A fine powder of vinylidene fluoride copolymer or a conductivity-imparting agent such as tin oxide or zinc oxide may be added.

It is desirable that the magnetic black toner according to the present invention contains a release agent. The intention is that by specifying the molecular weight distribution of the binder resin in an appropriate range, the offset resistance is good, and the dispersion state of the magnetic powder in the binder resin is good, and a high-density visible image is obtained. However, if the magnetic and non-magnetic toners are present on the same latent image carrier as in the configuration according to the present invention, the fixing properties between the two toners are different, and after the fixing, the layer is relatively thin. Since the surface of the magnetic toner layer is rougher than the surface of a non-magnetic toner capable of maintaining a smooth surface, when the transfer material such as paper and sheet is peeled off from the fixing heating roller, the separation may occur. The moldability must be even better, and the addition of an auxiliary release agent leads to a further improvement in fixability.

As described above, the release agent used in the present invention has a melting start temperature of 40 ° C. or higher, preferably 50 ° C.
C. or higher and 50 to 250 ° C. as measured by DSC, preferably having at least two or more melting points between 70 to 200 ° C., or two or more having different melting points can be mixed and used. . This is because if the melting start temperature of the release agent is lower than 40 ° C., the blocking resistance is poor, and those having a plurality of melting points between 50 and 250 ° C. release over a wider range from low to high temperatures. This is because a mold effect can be exhibited. Further, more preferable use methods of the release agent for the binder resin used in the present invention include two types of release agents having different melting points and having no polar group and a release agent having a polar group. It is desirable to use a combination of the above. This is because, when the binder resin of the present invention is used, most of the non-polar release agent is present in the matrix resin, and conversely, most of the release agent having a polar group is present in the domain resin. By doing so, it has a releasing effect on both the matrix resin and the domain resin. Therefore, it can be present in the matrix resin and the domain resin, and
As long as it has a plurality of melting points at 0 ° C., there is no problem even if one kind of release agent is used.

The following are examples of the releasing agent having no polar group used in the present invention. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof, and carnauba Examples of the wax include waxes mainly containing a fatty acid ester such as wax, sasol wax and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. The following are examples of the releasing agent having a polar group used in the present invention. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid, unsaturated fatty acids such as brandinic acid, eleostearic acid, and vinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, Saturated alcohols such as melisil alcohol, polyhydric alcohols such as sorbitol,
Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide, saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide, ethylene bis Oleic acid amide, hexamethylene bisoleic acid amide,
Unsaturated fatty acid amides such as N, N'-dioleyl adipamide, N, N'-dioleyl sebacamide, m-xylene bisstearic acid amide, N, N'-
Aromatic bisamides such as distearyl isophthalamide, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps), and aliphatic hydrocarbon waxes Waxes grafted with vinyl monomers such as styrene and acrylic acid, and partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols,
Examples thereof include methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

The amount of the release agent used in the present invention is desirably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin. If the amount of the release agent is 20 parts by weight or more, the blocking resistance and the high-temperature offset become poor. less than 1 part by weight,
No release effect.

These release agents are usually contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading.

In the multicolor developing method of sequentially forming an image on a latent image carrier using these full-color toners, in the present invention, the black toner is developed on the latent image carrier in the first order, From the eyes onward, it is desirable to sequentially develop cyan toner, yellow toner, and magenta toner to form multiple images.

The reason is that, when copying a pictorial image such as a full-color image, since the ultimate goal is to obtain an image as close as possible to a photograph, the obtained copied image may have some glossiness. Required. On the other hand, if a line image such as a black-and-white image has the level of gloss required for full color, it will be rather difficult to read, and glossiness is not required, and excellent toner characteristics against line image skipping and hollow spots Is required.

Therefore, in the case of the black-and-white combined use type copying machine according to the present invention, there are many occasions of obtaining a continuous copy image in a single black color, and so-called coalescence between particles is performed even with a low gloss toner. It is desirable to use a hard binder resin as a medium as the fixing property, and when copying a pictorial image such as full color, a clear color is required, and it is necessary to compare it to make it easier to mix colors. A binder resin that is easily melted is desired.

In the above case, in order to satisfy both, the influence of the surface gloss due to the difference of the binder resin as shown in FIG.

Thus, as in the conventional case, if the magenta toner is developed in the first order and the cyan, yellow, and black toners are successively developed, the multicolor development in the conventional development order is performed. After the development using the full-color toner of the present invention, when sequentially transferred onto a transfer paper such as paper, the black toner containing the magnetic material comes to the uppermost layer,
In the present invention, the glossiness of the three colors coming under the layer is hindered, and the glossiness of the full color image in which the four colors are superimposed results in different glossiness particularly at various parts of the image area. By sequentially obtaining a multicolor image, a low-gloss black toner is formed on the lowermost layer on the transfer paper, irregular reflection of light is prevented, and a full-color image having uniform gloss can be obtained.

The toner according to the present invention may be blended with a charge control agent for stabilizing the charge characteristics. At that time, a colorless or light-colored charge control agent that does not affect the color tone of the toner is preferable. In the present invention, the present invention is more effective when a negatively charged developer is used. In this case, examples of the negatively charged control agent include a metal complex of an alkyl-substituted salicylic acid (for example, chromium of di-tert-butylsalicylic acid). Complex or zinc complex). When the negative charge control agent is blended with the toner, the binder resin 100
0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight
It is better to add up to 8 parts by weight.

The method for measuring each physical property value according to the present invention will be described below.

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

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This is put in an aluminum pan, and an empty aluminum pan is used as a reference. First, the following operation is performed for the purpose of deleting the previous history. Room temperature to 200 in N ₂ atmosphere
The temperature is raised to 10 ° C at 10 ° C / min and kept at 200 ° C for 10 minutes. Thereafter, the mixture is rapidly cooled, the temperature is lowered to 10 ° C, and the temperature is kept at 10 ° C for 10 minutes. Then, at a heating rate of 10 ° C./min, 2
Raise the temperature to 00 ° C. In this heating process, the temperature is 40 to 10
An endothermic peak of the main peak in the range of 0 ° C. is obtained.

The intersection between the line of the middle point of the pace line before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention (see FIG. 2).

(2) GPC Measurement Method In the present invention, the molecular weight distribution of a chromatogram by GPC (gel permeation chromatography) using THF as a solvent is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected. Measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about 0 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As the column, a plurality of commercially available polystyrene gel columns are preferably combined, and for example, showex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

The sample is prepared as follows.

The sample is placed in THF, left for several hours, shaken sufficiently, mixed well with THF (until the sample is no longer united), and allowed to stand for 12 hours or more. At this time, TH
The time of leaving in F is set to 24 hours or more. Then, a sample processing filter (pore size 0.45 to
0.5 μm, for example, Myshoridisk H-25-
5 The product passed through Tosoh Co., Ltd., and can be used as a sample of GPC. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

(3) Measurement of hydroxyl value The hydroxyl value is measured by the following method according to the method shown in JIS K007.

In a 200 ml Erlenmeyer flask, place 6 g of the sample in 1 m
The mixture was precisely weighed in units of g, and a mixed solution of acetic anhydride / pyridine = 1/4 was added with a 5 ml hole pipette.
Add 1 with a measuring cylinder. A condenser is attached to the conical flask, and the reaction is carried out in an oil bath at 100 ° C. for 90 minutes.

Add 3 ml of distilled water from the top of the cooler, shake well, and let stand for 10 minutes. With the condenser still attached, the conical flask is pulled up from the oil bath and allowed to cool. When the temperature reaches about 30 ° C., the condenser and the flask port are washed with a small amount of acetone (about 10 ml) from the upper port of the condenser. THF50
The mixture is added with a graduated cylinder and neutralized with a N / 2KOH-THF solution using an alcohol solution of phenolphthalein as an indicator using a 50 ml (0.1 ml) burette. Immediately before neutralization end point, neutral alcohol 25ml
(Methanol / acetone = 1/1 volume ratio) and titration is performed until the solution shows a faint red color. A blank test is also performed at the same time.

Next, the hydroxyl value is determined according to the following equation.

[0159]

(Equation 2) Here, A: Number of ml of N / 2KOH-THF solution required for this test B: Number of ml of N / 2KOH-THF solution required for blank test f: Potency of N / 2KOH-THF solution S: Sample collection amount (G) C: acid value or alkali value. However, the acid value is plus and the alkali value is minus. An average value of two measured values is adopted.

(4) Gloss (Glossiness) Measuring Method Using a VG-10 type glossiness meter (manufactured by Nippon Denshoku Co., Ltd.), measurement is performed using each solid image used for chromaticity measurement as a sample.

First, the voltage was measured at 6 V using a constant voltage device.
Set to. Next, the light projection angle and the light reception angle are each 6
Adjust to 0 °.

Using the zero point adjustment and the standard plate, after setting the standard, place the sample image on the sample table,
Perform overlay measurement on the sheet, and read the numerical value shown in the marked part in%. At this time, the S, S / 10 switch SW is set to S, and the angle and sensitivity switch SW is set to 45-60.

A sample having an image density of 1.5 ± 0.1 is used.

[0164]

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

(Production of polyester resin) Production Example-1 2 mol of terephthalic acid, dodecenyl succinic anhydride 1.0
9 mol, polyoxypropylene (2.2) -2,2-
Bis (4-hydroxyphenyl) propane 3.4mo
l, Dibutyltin oxide (0.01 g) was placed in a glass 2-liter four-necked flask, fitted with a thermometer, a stirring rod, a condenser, and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and reacted at 170 ° C. for 5 hours.
Next, the temperature was raised to 190 ° C., and the reaction was performed for 4 hours. The hydroxyl value of the resin formed at this point was 59.8.

Thereafter, trimellitic anhydride 0.2 mol
l, and 0.08 g of dibutyltin oxide,
The mixture was further reacted at 3 ° C. for 3 hours, further heated to 200 ° C., and reacted for 5 hours to complete the reaction, thereby obtaining a polyester resin (Resin No. 1) of the present invention.

At that time, the hydroxyl value was 16.8, the glass transition temperature was 64 ° C., the weight average molecular weight was 16,000, the number average molecular weight was 5,900, and the ratio was 2.7. -Production Example-2 1.8 mol of isophthalic acid, 1.06 mol of dodecenyl succinic anhydride, polyoxypropylene (2.0)-
2,2-bis (4-hydroxyphenyl) propane
5 mol was reacted in a nitrogen atmosphere in the same manner as in Production Example-1. Then trimellitic anhydride 0.16mo
l, dibutyltin oxide (0.09 g) was added, and the reaction was carried out at 180 ° C for 5 hours.
o. 2) was obtained.

At that time, the hydroxyl value was 18.5, the glass transition temperature was 63 ° C., the weight average molecular weight was 17,000, the number average molecular weight was 5,800, and the ratio was about 2.9.
Met.・ Production Example-3 Terephthalic acid 2mol, Octylsuccinic acid 1.15mo
1, polyoxyethylene (2.0) -2,2-bis (4
-Hydroxyphenyl) propane was reacted in a nitrogen atmosphere in the same manner as in Production Example-1. Next, 0.18 mol of trimellitic anhydride and 0.08 g of dibutyltin oxide were added, and the reaction was carried out at 180 ° C. for 5 hours to obtain a polyester resin (Resin No. 3) of the present invention.

This resin has a hydroxyl value of 16.5, a glass transition temperature of 64 ° C., a weight average molecular weight (Mw) of 17000, and a number average molecular weight (Mn) of 6300, and Mw / Mn is about 2.
It was 7. Production Example-4 Polyoxypropylene (2.2) -2,2-bis (4-
Hydroxyphenyl) propane (5 mol), terephthalic acid (2 mol), trimellitic anhydride (3 mol), and dibutyltin oxide (0.05 g) were reacted at 220 ° C. in a nitrogen atmosphere using the same apparatus as in Production Example 1 to obtain a crosslinked polyester resin. (Resin No. 4) was obtained. The Mw / Mn of the obtained crosslinked polyester resin was clearly over 3.5.

(Production of Styrene-Acrylic Copolymer) Production Example-5 Styrene 70.00 parts by weight n-butyl acrylate 25.00 parts by weight Acrylic acid 5.00 parts by weight Di-tert-butyl peroxide 1. 50 parts by weight The above compound was added dropwise to 200 parts by weight of heated toluene over 4 hours. Further, the polymerization was completed under reflux of toluene, and toluene was removed while raising the temperature (120 ° C.) under reduced pressure.

The above resin 30.00 parts by weight Styrene 44.65 parts by weight N-butyl acrylate 20.00 parts by weight Mono-n-butylmale 5.00 parts by weight Divinylbenzene 0.35 parts by weight Benzoyl peroxide 1.20 parts by weight Di-tert-butyl peroxy-2-0.70 parts by weight Ethyl hexanoate
170 parts by weight of water in which 2 parts by weight were dissolved were added, and the mixture was vigorously stirred to obtain a suspension dispersion. The above-mentioned suspension dispersion was added to a reactor in which 50 parts by weight of water had been added and purged with nitrogen.
The suspension polymerization reaction was carried out for an hour. After the reaction, wash with water, dehydrate,
After drying, a styrene-acrylic copolymer resin (resin N
o. 5) was obtained. Production Example -6 Styrene 70.00 parts by weight n-Butyl acrylate 30.00 parts by weight Di-tert-butyl peroxide 1.00 parts by weight Solution polymerization was performed using the above compound in the same manner as in Production Example 5 to obtain a resin. Obtained.

The above resin 30.00 parts by weight Styrene 44.70 parts by weight n-butyl acrylate 20.00 parts by weight Mono-n-butyl maleate 3.00 parts by weight Divinylbenzene 0.40 parts by weight Benzoyl peroxide 1.30 parts by weight Di-tert-butylperoxy-2- 0.80 parts by weight Ethyl hexanoate Styrene-acrylic copolymer resin (resin No. 6) by performing suspension polymerization using the above mixture in the same manner as in Production Example-5. I got Production Example-7 Styrene 75.00 parts by weight n-butyl acrylate 20.00 parts by weight Methacrylic acid 5.00 parts by weight Di-tert-butyl peroxide 2.00 parts by weight Same as Production Example-5 using the above compound. Was subjected to solution polymerization to obtain a resin.

The above resin 30.00 parts by weight Styrene 44.65 parts by weight n-butyl acrylate 20.00 parts by weight Acrylic acid 5.00 parts by weight Divinylbenzene 0.35 parts by weight Benzoyl peroxide 1.00 parts by weight Di-tert -Butyl peroxy-2-0.70 parts by weight Ethyl hexanoate Using the above mixture, suspension polymerization was carried out in the same manner as in Production Example-5 to obtain a styrene-acrylic copolymer resin (Resin No. 7). . -Production Example-8 78.00 parts by weight of styrene 18.00 parts by weight of n-butyl acrylate 5.00 parts by weight of mono-n-butylmaleate 0.80 parts by weight of di-tert-butylperoxy-2-0.80 parts by weight of ethyl hexanoate The compound was dropped into 200 parts by weight of heated toluene over 4 hours. Further, the polymerization was completed under reflux of toluene, and the toluene was removed while raising the temperature (120 ° C.) under reduced pressure to obtain a styrene-acrylic copolymer resin (resin No. 1).
8) was obtained. Production Example-9 Styrene 75.00 parts by weight n-butyl acrylate 20.00 parts by weight Mono-n-butylmalate 5.00 parts by weight Di-tert-butyl peroxide 0.70 parts by weight The above compound was heated in toluene 200 It was added dropwise over 4 hours in parts by weight. Further, the polymerization was completed under reflux of toluene, and the resin No. 8 as No. 8. 8: The polymer was added to the reaction mixture so that the ratio of the polymer was 4: 6, and the mixture was thoroughly stirred. Toluene was removed while heating (120 ° C.) under reduced pressure to remove styrene.
An acrylic copolymer resin (Resin No. 9) was obtained. Production Example -10 90.00 parts by weight of styrene 10.00 parts by weight of n-butyl acrylate 7.00 parts by weight of di-tert-butyl peroxide Solution polymerization was carried out using the above compound in the same manner as in Production Example 5 to obtain a resin. Obtained.

The above resin 70.00 parts by weight Styrene 44.65 parts by weight n-butyl acrylate 20.00 parts by weight Mono-n-butylmale 5.00 parts by weight Divinylbenzene 0.35 parts by weight Benzoyl peroxide 1.00 parts by weight Di-tert-butylperoxy-2-0.70 parts by weight Ethyl hexanoate Styrene-acrylic copolymer resin (resin No. 10) by performing suspension polymerization using the above mixture in the same manner as in Production Example-5.
I got Production Example-11 Styrene 68.00 parts by weight n-butyl acrylate 22.70 parts by weight Mono-n-butylmalate 8.00 parts by weight Divinylbenzene 1.30 parts by weight di-tert-butylperoxyhexanoate 0.60 Parts by weight The above compound was added dropwise to 200 parts by weight of heated cumene over 4 hours. Further, polymerization was completed under the reflux of cumene, and cumene was removed while raising the temperature (200 ° C.) under reduced pressure to obtain a styrene-acrylic copolymer resin (Resin No. 11).

Example 1 100 parts by weight of a polyester resin (Resin No. 1) I. Pigment Yellow 17 3.5 parts by weight Di-tert-butylsalicylic acid 4 parts by weight was sufficiently premixed with a Henschel mixer,
The mixture was melt-kneaded in a twin-screw extruder, cooled, and coarsely ground to a particle size of about 1 to 2 mm using a hammer mill. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified by a multi-segment classifier to obtain yellow resin particles having a weight average particle size of 8.0 μm.

To 100 parts by weight of the above-mentioned yellow resin particles, 0.7 parts by weight of hydrophobic titanium oxide (BET 90 m ² / g) treated with nC ₄ H ₉ Si (OCH ₃ ) ₃ was added to obtain a yellow toner. And

Next, C.I. I. Instead of Pigment Yellow 17, a magenta toner was prepared in the same manner as the yellow toner using 4 parts by weight of a rhodamine pigment.

Next, C.I. I. Pigment Yellow 17 was replaced with 5 parts by weight of a phthalocyanine pigment represented by the following structural formula, and a cyan toner was obtained in the same manner as the yellow toner.

[0179]

Embedded image The yellow, magenta, and cyan toners are mixed with Cu-Zn-Fe-based ferrite particles whose surfaces are coated with a methyl methacrylate-butyl acrylate (75:25) copolymer so as to have a toner concentration of 5%, respectively, and developed. Agent.

Next, C.I. I. Pigment Yellow 17, FeO content 26.1%, specific surface area 8.1 m ² /
g, 60 parts by weight of magnetite having a bulk density of 0.44 g / cm ³ . Styrene-acrylic copolymer resin of No. 5 as a binder resin, 2.0 parts by weight of a low molecular weight polyethylene wax (melting point: 123 ° C., melting start temperature: 75 ° C.) and calcium laurate (106, 125) , 142, 160 ° C, melting point temperature 80 ° C), 2.0 parts by weight, and silica fine powder (BET 230 m ² / g) hydrophobized with hexamethyldisilazane as an additive. A black magnetic toner was obtained using 5 parts by weight.

The developing order of the toner is black, cyan,
Commercially available color copier modified to yellow and magenta (C
LC-500 Canon) and a developing contrast of 3
When the initial image was obtained at a constant voltage of 50 V, the color tone of the full-color image was excellent in chroma, and an image excellent in line reproducibility without dropping out of the toner particles and in the black-and-white image was obtained even in the black-and-white image.

The endurance test was carried out on both the full-color image and the black-and-white image at a fixing temperature of 170 ° C. for 80,000 sheets. As a result, no offset was generated on the fixing roller at all, and the original image with less fog was faithfully reproduced. was gotten.

Further, low temperature and low humidity (15 ° C./10% RH),
The charge amount was measured in an environment of high temperature and high humidity (32.5 ° C./85% RH).
c / g, -17.0 μc / g, and -1 for black and white durability, respectively.
The results were 2.3 μc / g and −10.2 μc / g, which were extremely low in environmental dependence.

Example 2 In Example 1, the polyester resin used for the yellow, magenta and cyan toners was resin No. 2, and the styrene-acrylic copolymer resin used for the black toner is resin No. The same evaluation as in Example 1 was carried out except that the sample of Example 6 was used. As a result, a full-color image having sufficient glossiness and a clear color tone and a black-and-white image excellent in reproducibility of fine lines were obtained. Was. The durability characteristics at this time are shown in Table 1, but no problem was found.

Example 3 In Example 1, the polyester resin used for the yellow, magenta and cyan toners was resin No. 3, and the styrene-acrylic copolymer resin used for the black toner is resin No. The same evaluation as in Example 1 was carried out except that the evaluation was 7, and a good initial image was obtained, and no problem was found in the physical property values in the durability evaluation as shown in Table 1.

Example 4 The styrene-acrylic copolymer resin used for the black toner was resin No. When the same evaluation as in Example 1 was performed except that the sample was set to 8, a full-color image having a clear color tone and a black-and-white image having a high image density were obtained. As shown in Table 1, durability characteristics and environmental characteristics were also improved. It was good.

Example 5 In Example 1, the polyester resin used for the yellow, magenta and cyan toners was resin No. 2, and the styrene-acrylic copolymer resin used for the black toner is resin No. When the same evaluation as in Example 1 was performed except that the value was set to 9, good results were obtained in both the initial image and the durability. Table 1 shows the results.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the developing order of the toner was changed to magenta, yellow, cyan, and black as in the prior art. Although the characteristics were good, the glossiness of the full-color image was as low as 6%, and only an image with a very poor texture was obtained as a pictorial image.
Table 1 shows the durability characteristics at this time.

Comparative Example 2 In Example 1, the resin used for the black toner was Resin No. Example 1 except that the polyester resin of No. 2 was used
In the initial evaluation, a full-color image having excellent color tone and a black-and-white image having high image density were obtained. However, when the durability evaluation was performed, an offset was generated after passing about 5,000 black-and-white images. I have. Table 1 shows the durability characteristics at this time.

Comparative Example 3 In Example 1, the polyester resin used for the yellow, magenta and cyan toners was resin No. 4, and the styrene-acrylic copolymer resin used for the black toner is resin No. The same evaluation as in Example 1 was performed except that the value was set to 10. As a result, offset occurred in 50,000 sheets of full-color image durability. Table 1 shows the durability characteristics at this time.

Comparative Example 4 The styrene-acrylic copolymer resin used in Example 1 for the black toner was resin No. The same evaluation as in Example 1 was performed except that the value was set to 11. However, at the time of the initial evaluation, black and white images were stuck, and offset occurred in 20,000 sheets of black single-color durability.

[0192]

[Table 1]

[0193]

According to the present invention, a binder resin component of a non-magnetic color toner and a magnetic black toner used in a full-color copying machine and a printer combined with a black-and-white machine is a polyester resin and a styrene-acrylic copolymer resin, respectively. In the magnetic black toner, the content of FeO in the magnetic powder to be used is regulated, and the release agent is contained in the toner, so that the non-magnetic toner can be used in the multi-color image in the non-magnetic toner layer. It is possible to improve the cleaning properties in a combined system of non-magnetic and magnetic toner by containing a fluidity improver and spherical fine particles as external additives. It became.

[Brief description of the drawings]

FIG. 1 is a diagram showing the effect of surface glossiness due to the difference in binder resin.

FIG. 2 is an explanatory diagram of a glass transition temperature in the present invention.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁷ Identification code FI G03G 9/08 325 331

Claims (4)

(57) [Claims] 1. A full-color toner for forming a color image by appropriately using at least one or more of a yellow toner, a magenta toner and a cyan toner together with a black toner, wherein the yellow toner, the magenta toner and the cyan toner are: A non-magnetic toner in which an external additive is externally added to colored resin particles in which a colorant is mixed and dispersed in a binder resin, wherein the black toner has a FeO content of 25% in magnetic iron oxide.
A magnetic toner in which an external additive is externally added to magnetic resin particles in which black magnetic powder and a release agent are mixed and dispersed in a binder resin in an amount of from 30 to 30% by weight; The binder resin used for the toner and the cyan toner includes the following components (a), (b),
(C) and (d ) (a) a divalent aromatic acid component (a) selected from isophthalic acid, terephthalic acid and derivatives thereof in an amount of 25 to 35 mol% of the total monomer amount, (b) trimellitic acid and The trivalent aromatic acid component (b) selected from the derivative is used in an amount of 2 to 4 mol based on the total amount of the monomers.
%, (C) a divalent acid component (c) selected at least from dodecenyl succinic acid, octyl succinic acid and its anhydride, 12 to 18 mol% of the total monomer amount, (d) propoxylation and / or ethoxylation. The etherified diphenol component (d) is used in an amount of 45 to 6 based on the total amount of the monomers.
A polyester resin produced from a monomer composition containing at least 0 mol%, wherein the polyester resin has a hydroxyl value of 10 to 20 and a weight average molecular weight of 13,000 to 2
0000 and a number average molecular weight of 5,000 to 8,000.
0, weight average molecular weight (Mw) / number average molecular weight (M
The ratio of n) is Ri der 2-3.5, the binder resin used in said black toner, the following components (e) and (f) (e) a dicarboxylic acid monoester monomer, a (f) divinyl benzene least Containing the divinylbenzene with the dicarbo
0.0 based on the content of the acid monoester monomer.
A styrene-acrylic copolymer resin produced from a monomer composition containing 1 to 5% by weight;
The acid value of the acrylic copolymer resin is 2 to 100 mgKOH
/ G, the acid value derived from the acid anhydride of the resin is 10 mgK
OH / g or less, and in the molecular weight distribution measured by GPC of the resin component, a region having a molecular weight of 5,000 or less is 15%
, Having a main peak in the region of molecular weight 5000 to 100,000, and having a weight average molecular weight of 5,000,000
A full-color toner of at least 00. 2. The release agent has a melting start temperature of 40.
C. or more, having a melting point of at least two or more between 50 and 250 ° C. as measured by DSC, or a release agent obtained by mixing two or more kinds having different melting points, 0.1 to 100 parts by weight of the release agent
The full-color toner according to claim 1, which is blended in an amount of 20 parts by weight. 3. A toner image is formed by developing an electrostatic latent image on an electrostatic image carrier using at least one of yellow toner, magenta toner and cyan toner appropriately and selectively with black toner. , it is transferred to successively transfer material the toner image in an image forming method for image formation, the yellow toner, the magenta toner, to claim 1 as a full color toner have a said cyan toner and the <br/> black toner An image forming method, comprising using the full-color toner described in the above. 4. The toner according to claim 1, wherein the yellow toner, the magenta toner,
The toner images on the latent image carrier are sequentially formed on a transfer material using the full- color toner having the cyan toner and the black toner.
In the image forming method of transferring to an image formed by developing the first order first on a transfer material said black toner, an image forming method according to claim 3, wherein to Rukoto image formation.